EP1696265A2 - Matériau pour l'enregistrement d'hologrammes, procédé d'enregistrement d'hologrammes, support d'enregistrement optique, et colorant correspondant - Google Patents

Matériau pour l'enregistrement d'hologrammes, procédé d'enregistrement d'hologrammes, support d'enregistrement optique, et colorant correspondant Download PDF

Info

Publication number
EP1696265A2
EP1696265A2 EP06003725A EP06003725A EP1696265A2 EP 1696265 A2 EP1696265 A2 EP 1696265A2 EP 06003725 A EP06003725 A EP 06003725A EP 06003725 A EP06003725 A EP 06003725A EP 1696265 A2 EP1696265 A2 EP 1696265A2
Authority
EP
European Patent Office
Prior art keywords
group
dye
hologram recording
hologram
light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06003725A
Other languages
German (de)
English (en)
Inventor
Hiroo Takizawa
Naoki Morinaga
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP1696265A2 publication Critical patent/EP1696265A2/fr
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/001—Phase modulating patterns, e.g. refractive index patterns

Definitions

  • the present invention relates to a hologram recording material and hologram recording method which can be applied to high density optical recording medium, three-dimensional display, holographic optical element, etc.
  • hologram The general principle of preparation of hologram is described in some literatures and technical books, e.g., Junpei Tsujiuchi, ''Holographic Display", Sangyo Tosho, Chapter 2.
  • a recording object is irradiated with one of two fluxes of coherent laser beams and a photosensitive hologram recording material is disposed in a position such that all the lights reflected by the recording object can be received.
  • the other coherent light is incident on the hologram recording material without hitting the object.
  • the light reflected by the object is called object light.
  • the light with which the recording material is directly irradiated is called reference light.
  • the band of interference of reference light with object light is then recorded as image data.
  • the hologram recording material thus processed is irradiated with the same light (reproducing light) as the reference light, the hologram performs diffraction in such a manner that the wave front of the first reflected light which has reached the recording material from the object during recording is reproduced.
  • substantially the same object image as the real image of the object can be three-dimensionally observed.
  • the hologram formed by allowing reference light and object light to be incident on the hologram recording material in the same direction is called transmission hologram.
  • the interference fringes are formed in the direction perpendicular or substantially perpendicular to the surface of the recording material at an interval of from about 1,000 to 3,000 lines per mm.
  • the hologram formed by allowing reference light and object light to be incident on the hologram recording material in opposite directions is normally called reflection hologram.
  • the interference fringes are formed in the direction parallel to or substantially parallel to the surface of the recording material at an interval of from about 3,000 to 7,000 lines per mm.
  • the transmission hologram can be prepared by any known method as disclosed in JP-A-6-43634.
  • the reflection hologram can be prepared by any known method as disclosed in JP-A-2-3082, JP-A-3-50588, etc.
  • the hologram having a sufficiently thick layer relative to the interval of interference fringes (normally five times the interval of interference fringes or about 1 ⁇ m or more) is called volume hologram.
  • the hologram having a layer thickness which is five times or less the interval of interference fringes or about 1 ⁇ m or less is called plane or surface hologram.
  • the hologram involving the absorption by dye or silver causing the recording of an interference fringes is called amplified hologram.
  • the hologram involving recording by surface relief or refractive index modulation is called phase hologram.
  • the amplified hologram is subject to drastic drop of light diffraction efficiency or reflectance due to absorption of light and thus is disadvantageous in percent utilization of light.
  • the phase hologram is preferably used.
  • volume phase type hologram many interference fringess having different refractive indexes are formed in the hologram recording material without by making optical absorption, making it possible to modulate the phase of light without absorbing light.
  • the reflection volume phase type hologram is also called Lipman type hologram.
  • wavelength-selective reflection involving Bragg diffraction allows the formation of full-color image, reproduction of white color and enhancement of resolution at a high diffraction efficiency, making it possible to provide a high resolution full-color three-dimensional display.
  • hologram has been put into practical use in the art of holographic optical element (HOE) such as headup display (HUD) to be mounted on automobile, pickup lens for optical disc, head mount display, color filter for liquid crystal and reflection type liquid crystal reflector by making the use of its wavelength-selective reflectivity.
  • HOE holographic optical element
  • an ultrahigh density recording medium capable of recording data having a capacity of about 1 TB or more at a high rate and reduced cost has been desired also in business uses such as computer backup and broadcast backup.
  • three-dimensional optical recording media which perform recording in the thickness direction have been recently noted as ultimate ultrahigh density recording media.
  • Effective methods for this system include method involving the use of two-photon absorbing material and method involving the use of holography (interference). Therefore, volume phase type hologram recording materials have recently been suddenly noted as three-dimensional optical recording media (holographic memory).
  • the holographic memory comprising a volume phase type hologram recording material records many two-dimensional digital data (called signal light) using a spatial light modulation element (SLM) such as DMD and LCD instead of object light reflected by the three-dimensional object.
  • SLM spatial light modulation element
  • the recording involves multiplexed recording such as angle-multiplexed recording, phase-multiplexed recording, wavelength-multiplexed recording and shift-multiplexed recording, a capacity as high as up to I TB can be attained.
  • reading is normally accomplished by the use of CCD, CMOS or the like. These elements allow parallel writing/reading, making it possible to raise the transfer rate up to 1 Gbps.
  • the hologram recording materials to be used in holographic memory have severer requirements than for the three-dimensional display and HOE as follows.
  • volume phase type hologram recording materials examples include write-once-read-many type hologram recording materials such as gelatin bichromate process hologram recording material, bleached silver halide process hologram recording material and photopolymer process hologram recording material and rewritable type hologram recording materials such as photorefractive process hologram recording material and photochromic polymer process hologram recording material.
  • the gelatin bichromate process hologram recording material is advantageous in that it has a high diffraction efficiency and a low noise but is disadvantageous in that it has extremely poor storage properties, requires wet processing and exhibits a low sensitivity.
  • the gelatin bichromate process hologram recording material is not suitable for holographic memory.
  • the bleached silver halide process hologram recording material is advantageous in that it has a high sensitivity but is disadvantageous in that it requires wet processing and troublesome bleaching process, causes great scattering and has a poor light-resistance.
  • the bleached silver halide process hologram recording material too, is not suitable for holographic memory.
  • the photorefractive hologram recording material is advantageous in that it is rewritable but is disadvantageous in that it requires the application of a high electric field during recording and has poor record storage properties.
  • the photochromic polymer process hologram recording material such as azobenzene polymer process hologram recording material is advantageous in that it is rewritable but is disadvantageous in that it has an extremely low sensitivity and poor record storage properties.
  • WO974436SAI proposes a rewritable hologram recording material utilizing the refractive anisotropy and orientation control of azobenzene polymer (photochromic polymer).
  • this type of a rewritable hologram recording material is disadvantageous in that since the quantum yield of isomerization of azobenzene is low and this process involves orientation change, the sensitivity is extremely low.
  • This type of a rewritable hologram recording material is also disadvantageous in that it has poor record storage properties, which are contrary to rewritability. Thus, this type of a rewritable hologram recording material cannot be put into practical use.
  • the dry-processed photopolymer process hologram recording material disclosed in the above cited JP-A-6-43634, JP-A-2-3082 and JP-A-3-50588 has the following arrangement.
  • the dry-processed photopolymer process hologram recording material is essentially composed of a binder, a radical-polymerizable monomer and a photopolymetizafion initiator.
  • one of the binder and the radical-polymerizable monomer comprises a compound having an aromatic ring, chlorine or bromine incorporated therein to make a difference in refractive index therebetween.
  • the hologram exposure causes the progress of polymerization with the monomer and the binder gathering at the bright area and the dark area of the interference fringes thus formed, making it possible to form a refractive index difference.
  • the dry-processed photopolymer process hologram recording material is a relatively practical hologram recording material which can attain a high diffraction efficiency and dry processing properties at the same time.
  • the dry-processed photopolymer process hologram recording material is disadvantageous in that it has a sensitivity of about one thousandth of that of the bleached silver halide process hologram recording material, requires a heat-fixing step for about 2 hours to enhance diffraction efficiency, requires radical polymerization causing the effect of polymerization inhibition by oxygen and is subject to shrinkage after exposure and fixing and hence change of diffraction wavelength and angle during reproduction.
  • the dry-processed photopolymer process hologram recording material is in the form of soft membrane and lacks storage properties. Accordingly, the dry-processed photopolymer process hologram recording material can be by no means used for holographic memory.
  • cationic polymerization particularly cationic polymerization involving the ring opening of an epoxy compound, etc., causes little shrinkage after polymerization and no polymerization inhibition by oxygen. As a result, a rigid membrane can be given. It is also pointed out that cationic polymerization is more suitable for holographic memory than radical polymerization.
  • JP-A-5-107999 and JP-A-8-16078 disclose a hologram recording material comprising in combination a cationically-polymerizable compound (monomer or oligomer) instead of binder and a sensitizing dye, a radical polymerization initiator, a cationic polymerization initiator and a radical-polymerizable compound.
  • JP-T-2001-523842 and JP-T-11-512847 disclose a hologram recording material comprising only a sensitizing dye, a cationic polymerization initiator, a cationically-polymerizable compound and a binder but free from radical polymerization.
  • the aforementioned cationic polymerization process hologram recording material shows some improvement in shrinkage resistance as compared with the radical polymerization process hologram recording material but has a lowered sensitivity as opposed to the improvement. It is thought that this disadvantage gives a great problem in transfer rate during practical use. Further, the cationic polymerization process hologram recording material exhibits a reduced diffraction efficiency that probably gives a great problem in S/N ratio and multiplexed recording properties.
  • the photopolymer process hologram recording method involves the movement of materials. This causes a dilemma, In some detail, when the hologram recording material to be applied to holographic memory is arranged to have better storage properties and shrinkage resistance, the resulting sensitivity is lowered (cationic polymerization process hologram recording material). On the contrary, when the hologram recording material is arranged to have an enhanced sensitivity, the resulting storage properties and shrinkage resistance are deteriorated (radical polymerization process hologram recording material). In order to enhance the recording density of holographic memory, it is essential that multiplexed recording involving more than 50 times, preferably 100 times or more recording jobs be effected.
  • the photopolymer process hologram recording material employs polymerization process involving the movement of materials to perform recording
  • the recording speed in the latter half of multiplexed recording process, in which most of the compound has been polymerized is reduced as compared with that in the initial stage of multiplexed recording process. Accordingly, exposure must be adjusted and a broad dynamic range must be used to control the recording speed. This gives a practically great problem.
  • An object of an illustrative, non-limiting embodiment of the invention is to provide a hologram recording material and hologram recording method which can be applied to high density optical recording medium, three-dimensional display, holographic optical element, etc. and can attain a high sensitivity, high diffraction efficiency, good storage properties, low shrinkage factor, dry processing properties and multiplexed recording properties (high recording density) at the same time.
  • Another object of an illustrative, non-limiting embodiment of the invention is to provide a hologram recording material which undergoes no deterioration even when irradiated with reproducing light after recording, i.e., so-called fixed hologram recording material which allows non-destructive reproduction and thus exhibits excellent storage properties.
  • Another object of an illustrative, non-limiting embodiment of the invention is to provide a hologram recording material which, when fixed after recording, does not absorb hologram reproduction wavelength, making it possible to obtain a high absolute diffraction efficiency.
  • the hologram recording material comprising an optically self-discolorable sensitizing dye of the invention undergoes decomposition of the sensitizing dye, making it possible to avoid deterioration even when irradiated with reproducing light, i.e., allowing non-destructive reproduction and providing excellent storage properties.
  • the hologram recording material of the invention absorbs no hologram reproducing light after fixing, making it possible to obtain a high absolute diffraction efficiency.
  • the hologram recording material of the invention which undergoes, little shrinkage during recording and shows a linear rise of diffraction efficiency with exposure, making it possible to perform hologram recording as well.
  • the hologram recording material and recording/reproduction method of the invention can be applied to holographic memory, etc. to advantage from the standpoint of capacity, storage properties, system simplification, etc.
  • Fig. 1 is a schematic diagram illustrating a two-flux optical system for hologram exposure.
  • 10 YAG laser; 12: Laser beam; 14: Mirror; 20: Beam splitter; 22: Beam segment 24: Mirror; 26: Spatial filter; 28: Sample; 30: Hologram recording material; 32: He-Ne laser beam; 34: He-Ne laser, 36: Detector, 38: Rotary stage; 40: Beam expander; and 42: Fixing xenon lamp + band pass filter.
  • a hologram recording material of the invention includes at least: a sensitizing dye represented by the following formula (1), capable of absorbing hologram recording light to generate an excited state thereof and discoloring itself upon irradiation after hologram recording; and an interference fringe-recording component capable of recording interference fringes as a retractive index modulation by an energy or electron transfer from the excited state: D-L-E-LP (1)
  • D represents a group containing a sensitizing dye.
  • the sensitizing dye include those which absorb any of ultraviolet rays, visible light and infrared rays having a wavelength range of from 200 to 2,000 mn, preferably ultraviolet rays and visible light having a wavelength range of from 300 to 700 nm, more preferably visible light having a wavelength range of from 400 to 700 nm to generate excited state.
  • Preferred examples of the sensitizing dye contained in D include cyanine dye, squarilium cyanine dye, styryl dye, pyrilium dye, melocyanine dye, benzylidine dye, oxonol dye, azlenium dye, coumarine dye, ketocoumarine dye, styrylcoumarinc dye, pyrane dye, xanthene dye, thioxanthene dye, phenothiazine dye, phenoxazine dye, phenazine dye, phthalocyanine dye, azaporphyrin dye, porphyrin dye, condensed aromatic dye, perylene dye, azomethine dye, anthraquinone dye, metal complex dye, and metaloccne dye.
  • sensitizing dyes More desirable among these sensitizing dyes are cyanine dye, squarilium cyanine dye, pyrilium dye, melocyanine dye, oxonol dye, coumarine dye, ketocoumarine dye, styrylcoumarine dye, pyrane dye, xanthene dye, thioxanthene dye, condensed aromatic dye, metal complex dye, and metalocene dye.
  • Even more desirable among these sensitizing dyes are cyanine dye, melocyanine dye, oxonol dye, benzylidne dye, and styryl dye.
  • metal complex dyes Ru complex dyes are particularly preferred.
  • metalocene dyes ferrocenes are particularly preferred.
  • sensitizing dyes and dyestuffs disclosed in Sinya Ogawara, “Shikiso Handobukku (Handbook of Dyes)", Kodansha, 1986, Shinya Ogawara, “Kinosei Shikiso no Kagaku (Chemistry of Functional Dyes)", CMC, 1981, and Tadasaburo Ikemori, “Tokushu Kino Zairyo (Specially Functional Materials)", CMC, 1986 may be used as sensitizing dye of the invention.
  • the sensitizing dye to be used in the invention is not limited to these examples. Any dye or dyestuff may be used so far as it absorbs light in the visible range. These sensitizing dyes may be selected such that they are adapted for the wavelength of radiation from the light source depending on the purpose. Two or more sensitizing dyes may be used in combination depending on the purpose.
  • the molar absorption coefficient of the sensitizing dye at the wavelength of hologram exposure is preferably reduced to maximize the added amount of the sensitizing dye for the purpose of enhancing sensitivity.
  • the molar absorption coefficient of the sensitizing dye at the wavelength of hologram exposure is preferably from not smaller than 1 to not greater than 10,000, more preferably from not smaller than 1 to not greater than 5,000, even more preferably from not smaller than 5 to not greater than 2,500, most preferably from not smaller than 10 to not greater than 1,000.
  • the transmittance of the hologram recording material at the recording wavelength is preferably from 10% to 99%, more preferably from 20% to 95%, even more preferably from 30% to 90%, particularly from 40% to 85% from the standpoint of diffraction efficiency, sensitivity and recording density (multiplexity).
  • the molar absorption coefficient of the sensitizing dye at the recording wavelength and the molarity of the sensitizing dye to be added are preferably adjusted according to the thickness of the hologram recording material.
  • ⁇ max of the sensitizing dye is preferably shorter than the wavelength of hologram recording, more preferably between the wavelength of hologram recording and the wavelength of 100 nm shorter than the wavelength of hologram recording.
  • the molar absorption coefficient of the sensitizing dye at the recording wavelength is preferably one fifth or less, more preferably one tenth or less of that at ⁇ max.
  • the sensitizing dye is an organic dye such as cyanine dye and melocyanine dye
  • the molar absorption coefficient of the sensitizing dye at the recording wavelength is more preferably one twenticth or less, even more preferably one fiftieth or less, particularly one hundredth or less of that at ⁇ max.
  • the sensitizing dye contained in D is discolored by E which is disconnected from LP when irradiated with light.
  • the term "discoloration" as used herein is meant to indicate that either of, preferably both of, the shifting of ⁇ max to shorter wavelength and the drop of molar absorption coefficient occur.
  • the molar absorption coefficient of the dye represented by the formula (1) of the invention at the wavelength of hologram reproducing light for the dye represented by the formula (1) after optical self-discoloration reaction is preferably 2,500 or less, more preferably 1,000 or less, even more preferably 500 or less, most preferably 100 or less.
  • the sensitizing dye contained in D may be connected to L at any site thereof
  • L represents a mere bond or connecting group.
  • the connecting group represented by L may be any connecting group, preferably a connecting group having from 0 to 100, preferably from not smaller than 1 to not greater than 20 carbon atoms formed by singly or in combination alkylene group (preferably alkylene group having from 1 to 20 carbon atoms such as methylene, ethylene, butylene, pentylene, hexylene and octylene), arylene group (preferably C 6 -C 26 arylene group such as phenylene and naphthylene), alkenylene group (preferably C 2 -C 20 alkenylene group such as ethenylene and propenylene), alkinylene group (preferably C 2 -C 20 alkinylene group such as ethynylene and propynylene), amide group, ester group, sulfamide group, sulfonic acid ester group, ureido group, sulfonyl group, sulfiny
  • E represents a site at which the sensitizing dye can be discolored when the molecule is disconnected from LP.
  • E is preferably a site at which a nucleophilic agent, electrophilic agent or radical, more preferably nucleophilic agent is generated when disconnected from LP.
  • the nucleophilic agent thus generated is more preferably any of -S-, -SH, -O-, -OH and -NHR 31 , even more preferably any of -S- and -SH
  • R 31 represents a hydrogen atom, alkyl group (preferably C 1 -C 20 alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxylmethyl and 5-carboxypentyl), alkenyl group (preferably C 2 -C 20 alkenyl group such as vinyl, allyl, 2-butenyl, 1,3-butadienyl), cycloalkyl group (preferably C 3 -C 20 cycloalkyl group such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylophenyl and 1-nap
  • LP represents a group containing a site at which the molecule can be disconnected from E when the interference ninge-recording component is irradiated with light.
  • the light with which the interference fringe-recording component is irradiated is preferably any of ultraviolet ray, visible light and infrared ray having a wavelength of from 200 to 2,000 nm, more preferably ultraviolet ray or visible light having a wavelength of from 250 to 700 nm.
  • the interference fringe-recording component is preferably irradiated with light having a wavelength different from that of hologram recording light.
  • LP is preferably represented by the following formula (2):
  • R 32 represents a substituent.
  • Preferred examples of the substituent R 32 include alkyl group (preferably alkyl group having from 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, and 5-carboxypentyl), alkenyl groups (preferably alkenyl group having from 2 to 20 carbon atoms such as vinyl, allyl 2-butenyl and 1,3-butadienyl), cycloalkyl groups (preferably cycloalkyl group having from 3 to 20 carbon atoms such as cyclopentyl and cyclohexyl), aryl groups (preferably aryl group having from 6 to 20 carbon atoms such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-na
  • alkyl groups alkenyl groups, aryl groups, alkinyl groups, halogen atoms, amino groups, nitro groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, acylamino groups, acyloxy groups, carbamoyl groups, and alkoxycarbonyl groups.
  • alkyl groups alkenyl groups, aryl groups, alkinyl groups, halogen atoms, amino groups, nitro groups, alkoxy groups, aryloxy groups, acylamino groups, and acyloxy groups.
  • one or more nitro groups or alkoxy groups are incorporated.
  • the alkoxy group is more preferably a methoxy group.
  • R 33 and R 34 each independently represent a hydrogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group or acyl group (Preferred examples of these groups include those listed above with reference to R 32 ).
  • R 33 is preferably any of hydrogen atom, alkyl group, aryl group and acyl group.
  • the aryl group represented by R 33 is more preferably 2-nitroophenyl group.
  • the acyl group represented by R 33 is more preferably benzoyl group, even more preferably substituted by alkoxy group.
  • R 34 is preferably a hydrogen atom or alkoxy group.
  • the suffix a1 represents an integer of from 1 to 5, preferably from 1 to 3.
  • the plurality of R 32 's may be the same or different and may be connected to each other to form a ring.
  • Preferred examples of the ring thus formed include benzene ring and pyridine ring.
  • R 32 is a nitro group
  • the nitro group when a1 is 1, the nitro group is preferably on the 2-position.
  • the nitro group is preferably on the 2- or 6-position.
  • R 32 is an alkoxy group
  • a1 is preferably 2 or more.
  • the alkoxy group is preferably on the 3- or 4-position.
  • the sensitizing dye represented by the formula (1) is more preferably represented by any of the formulae (3-1) to (3-5).
  • the dyes represented by the formula (3-1) are generically called cyanine dye.
  • the dyes represented by the formula (3-2) arc generically called melocyanine dye.
  • the dyes represented by the formula (3-3) are generically called oxonol dye.
  • the dyes represented by the formula (3-4) are generically called benzylidene dye.
  • the dyes represented by the formula (3-5) are generically called styryl dye.
  • Za 1 , Za 2 , Za 3 and Za 8 each independently represent an atomic group constituting a 5-membered or 6-membered nitrogen-containing heterocyclic ring.
  • Preferred examples of the atomic group include C 3 -C 25 oxazole nucleus (e.g., 2-3-methyloxazolyl, 2-3-ethyloxazolyl, 2-3,4-diethyloxazolyl, 2-3-methylbenzooxazolyl, 2-3-ethylbenzooxazolyl, 2-3-sulfoethylbenzooxazolyl, 2-3-sulfopropylbenzooxazolyl, 2-3-methylthioethyl benzooaxazolyl, 2-3-methoxyethylbenzooxazolyl, 2-3-sulfobutylbenzooxazolyl, 2-3-methyl- ⁇ -naphthooxazolyl, 2-3-methyl- ⁇ -n
  • C 10 -C 30 indolenine nucleus e.g., 3,3-dimethyl-1-pentylindolenine, 3.3-dimethyl-1-mlfoproopyl indolenine, 5-carbmcy-1,3,3 trimethylindolenine, 5-carbamoyl-1,3,3-trimethylindolenine, 1,3,3 trimethyl-4,5-benzoindolenine
  • C 9 -C 25 quinoline nucleus e.g., 2-1-methylquinolyl, 2-1-ethylquinolyl, 2-1-methyl-6-chlloroquinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1-
  • atomic group examples include thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotellurazole nucleus, imidazoline nucleus, imidazo(4,5-quinozaline) nucleus, oxadiazole nucleus, thiadiazote nucleus, tetrazole nucleus, and pyrimidine nucleus.
  • substituents on these atomic groups include alkyl group (e.g., methyl, ethyl, propyl), halogen atom (e.g., chlorine, bromine, iodine, fluorine), nitro group, alkoxy group (e.g., methoxy, ethoxy), aryl group (e.g., phenyl), heterocyclic group (e.g., 2-pyridyl, 3-pyridyl, 1-pyrrolyl, 2-chenyl), aryloxy group (e.g., phenoxy), acylamino group (e.g., acetylamino, benzoylamino), carbamoyl group (e.g., N,N-dimethylcarbamoyl), sulfo group, sulfonamide group (e.g., methanesulfonamide), sulfamoyl group (e.g.
  • substituents are oxazole nucleus, imidazole nucleus, and thiazole nucleus. These heterocyclic rings may be further substituted. Examples of rings which can be condensed to these heterocyclic rings include benzene ring, benzofurane ring, pyridine ring, pyrrole ring, indole ring, and thiophene ring.
  • the ring formed by Za 1 or Za 2 is preferably a benzooxazole ring.
  • Za 4 to Za 7 each independently represent an atomic group constituting a 5-membered or 6-membered ring, preferably an atomic group required to form an acidic nucleus, as defined in James, The Theory of the Photographic Process", 4th ed., Macmillan Inc., 1977, page 198.
  • the atomic group include nuclei such as 2-pyrazolone-5-one, pyrazolidino-3,5-diono, imidazoline-5-one, hydantoin, 2-thiohydantoin, 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5-one, 2-thooxazoline-2,4-dione, isorhodanine, rhodanine, indane-1,3-dione, thiophene-3-one, thiophene-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo(3,2-a)pyrimidine, 3,4-dihydro isoquinoline-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobar
  • Preferred among these nuclei are pyrazolidino-3,5-dione, rhodanine, indane-1,3-dione, thiophene-3-one, thiophene-3-one-1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, and 2-thiobarbituric acid.
  • Ra 1 , Ra 2 , Ra 3 and Ra 5 each independently represent a hydrogen atom, alkyl group, alkenyl group, aryl group or heterocyclic group (Preferred examples of these groups include those listed above with reference to R 32 ), preferably alkyl group.
  • Ra 4 and Ra 6 each independently represent a substituent (Preferred examples of the substituent include those listed above with reference to R 32 ), preferably an alkyl group, alkenyl group, aryl group, heterocyclic group, halogen atom, amino group, cyano group, nitro group, hydroxyl group, alkoxy group, aryloxy group, carbamoyl group, acylamino group or alkoxycarbonyl group, more preferably an alkyl group, alkenyl group, amino group, hydroxyl group, alkoxy group, aryloxy group or acylamino group.
  • Ma 1 to Ma 21 each independently represent a methine group which may have substituents.
  • substituents include C 1 -C 20 alkyl group (e.g., methyl, ethyl, i-propyl), halogen atom (e.g., chlorine, bromine, iodine, fluorine), nitro group, C 7- C 20 alkoxy group (e.g., methoxy, ethoxy), C 6 -C 26 aryl group (e.g., phenyl, 2-naphthyl), C 0 -C 20 heterocyclic group (e.g., 2-pyridyl, 3-pyridyl), C 6 -C 20 aryloxy group (e.g., phenoxy, 1-naphthoxy, 2-naphthoxy), C 1 -C 20 acylamino group (e.g., acetylamino, benzoyla
  • C 1 -C 20 alkyl group
  • substituents may form a ring with other methine groups or chromophores, preferably unsubstituted methine group, ethyl-substituted methine group or methyl-substituted methine group.
  • na 1 , na 2 , na 3 and na 5 each independently represent 0 or 1, preferably 0.
  • na 4 and na 6 each independently represent an integer of from 0 to 5.
  • the plurality of Ra 4 's may be the same or different and may be connected to each other to form a ring.
  • the ring thus formed is preferably a benzene ring or pyridine ring.
  • the plurality of Ra 6 's may be the same or different and may be connected to each other to form a ring.
  • the ring thus formed is preferably a benzene ring or pyridine ring.
  • ka 1 to ka 5 each independently represent an integer of from 0 to 3, preferably an integer of 0 to 2.
  • the plurality of Ma 3 's and Ma 4 's may be the same or different.
  • the plurality of Ma 10 's and Ma 11 's may be the same or different.
  • the plurality of Ma 12 's and Ma 13 's may be the same or different.
  • the plurality of Ma 16 's and Ma 17 's may be the same or different.
  • ka 5 is 2 or more, the plurality of Ma 20 's and Ma 21 's may be the same or different.
  • the suffixes ka 1 , ka 2 , ka 3 , ka 4 and ka 5 are preferably 0 or 1, from 0 to 2, 0 or 1, 0 or 1 and 1 or 2, respectively.
  • CI represents an ion that neutralizes electric charge.
  • suffix y represents the number of CI's required to neutralize electric charge.
  • the sensitizing dye represented by the formula (3-1) comprises a group represented by the formula (4) incorporated in any of Ra 1 , Ra 2 and Ma 3 to Ma 5 , preferably Ra 1 or Ra 2
  • the sensitizing dye represented by the formula (3-2) comprises a group represented by the following formula (4) incmpornted in any of Ra 3 , Ma 10 and Ma 11 , preferably Ra 3
  • the sensitizing dye represented by the formula (3-3) comprises a group represented by the following formula (4) incorporated in any of Ma 12 to Ma 14
  • the sensitizing dye represented by the formula (3-4) comprises a group represented by the following formula (4) incorporated in any of Ra 4 , Ma 16 and Ma 17
  • the sensitizing dye represented by the formula (3-5) comprises a group represented by the following formula (4) incorporated in any of Ra 5 , Ra 6 , Ma 20 and Ma 21 , preferably Ra 5 .
  • R 32 , R 33 , R 34 and a1 are as defined in the formula (2); E1 represents -O-, -S- or -NR 31 -, preferably -S-; and R 31 represents a hydrogen atom, alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group.
  • the group represented by the formula (4) is more preferably represented by any of the following formulae (6-1) to (6-3). wherein El is as defined in the formula (4).
  • R 35 represents a hydrogen atom, alkyl group or aryl group (Preferred examples of these groups include those listed above with reference to R 33 ), preferably hydrogen atom, methyl group or 2-nitrophenyl group.
  • R 36 represents a substituent (Preferred examples of these groups include those listed above with reference to R 33 ), preferably alkyl group, alkenyl group, aryl group, alkinyl group, halogen atom, amino group, nitro group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, acyloxy group, carbamoyl group or alkoxycarbonyl group, more preferably alkyl group, alkenyl group, aryl group, alkinyl group, halogen atom, amino group, nitro group, alkoxy group, aryloxy group, acyloxy group, acylamino group or acyloxy group, even more preferably nitro group or alkoxy group.
  • the suffix a2 represents an integer of from 0 to 4, preferably from 0 to 2.
  • the plurality of R 36 's may be the same or different and may be connected to each other to form a ring.
  • the ring thus formed is preferably a benzene ring or pyridine ring.
  • R 36 is a nitro group, it is preferably on the 6-position.
  • R 36 is an alkoxy group, it is preferably on the 4- or 5-position.
  • R 37 and R 38 each independently represent a hydrogen atom or alkyl group, preferably hydrogen atom or methyl group
  • R 39 and R 40 each independently represent an alkyl group, preferably methyl group
  • R 41 represents a substituent (Preferred examples of these groups include those listed above with reference to R 36 ).
  • the suffix a3 represents an integer of from 0 to 3, preferably 0 or 1.
  • the plurality of R 41 's may be same or different and may be connected to each other to form a ring.
  • the ring thus formed is preferably a benzene ring or pyridine ring.
  • R 42 and R 43 each independently represent a substituent (Preferred examples of these groups include those listed above with reference to R 36 ), preferably nitro group or alkoxy group, more preferably alkoxy group, most preferably methoxy group.
  • the suffixes a4 and a5 each independently represent an integer of from 0 to 5, preferably from 0 to 2.
  • the plurality of R 42 's may be same or different and may be connected to each other to form a ring.
  • the ring thus formed is preferably a benzene ring or pyridine ring,
  • the plurality of R 43 's may be same or different and may be connected to each other to form a ring.
  • the ring thus formed is preferably a benzene ring or pyridine ring.
  • the sensitizing dye represented by the formula (1) of the invention is preferably represented by any of the formulae (3-1), (3-2) and (3-4), more preferably any of the formulae (3-1) and (3-2), most preferably the formula (3-1).
  • the sensitizing dye represented by the formula (1) is more preferably represented by the following formula (7-1) or (7-2).
  • Ra 1 to Ra 3 , ka 1 , ka 2 , Za 4 , CI and y are as defined in the formulae (3-1) and (3-2).
  • X 1 to X 3 each independently represent -O-, -S-, -NR 20 - or-CRa 21 R 22 -, preferably -O-, -S- or -NR 20 -.
  • R 20 to R 22 each independently represent a hydrogen atom, alkyl group, alkenyl group, aryl group or heterocyclic group (Preferred examples of these groups include those listed above with reference to Ra 1 ), preferably hydrogen atom, alkyl group or aryl group, more preferably alkyl group.
  • X 1 and X 2 each are more preferably -O-.
  • Ra 12 to Ra 14 , Ra 17 and Ra 18 each independently represent a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, halogen atom, nitro group, alkoxy group, aryloxy group, acylamino group, carbamoyl group, hydroxyl group, alkylthio group or cyano group, preferably hydrogen atom, alkyl group, aryl group, heterocyclic group, halogen atom, alkoxy group or aryloxy group, more preferably hydrogen atom or alkyl group, even more preferably hydrogen atom, methyl group or ethyl group.
  • Ra 15 , Ra 16 and Ra 19 each independently represent a substituent, preferably alkyl group, aryl group, heterocyclic group, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfamoyl group, carbamoyl group, acylamino group or alkoxycarbonyl group, more preferably alkyl group, aryl group, heterocyclic group, halogen atom or alkoxy group.
  • na 7 to na 9 each independently represent an integer of from 0 to 5, preferably from 0 to 2.
  • the plurality of Ra 15 's may be the same or different and may be connected to each other to form a ring.
  • Preferred examples of the ring thus formed include benzene ring, benzofurane ring, pyridine ring, pyrrole ring, indole ring, and thiophene ring.
  • the plurality of Ra 16 's may be the same or different and may be connected to each other to form a ring.
  • Preferred examples of the ring thus formed include benzene ring, benzofurane ring, pyridine ring, pyrrole ring, indole ring, and thiophene ring.
  • the plurality of Ra 19 's may be the same or different and may be connected to each other to form a ring.
  • Preferred examples of the ring thus formed include benzene ring, benzofurane ring, pyridine ring, pyrrole ring, indole ring, and thiophene ring.
  • the plurality of Ra 12 's and Ra 13 's may be the same or different and when ka 2 is 2 or more, the plurality of Ra 17 's and Ra 18 's may be the same or different.
  • the suffix ka 1 is preferably 0 or 1 and the suffix ka 2 is preferably from 0 to 2.
  • the sensitizing dye represented by the formula (7-1) comprises a group represented by the formula (4) incorporated in any of Ra 1 , Ra 2 and Ra 12 to Ra 14 , preferably Ra 1 or Ra 2 and the sensitizing dye represented by the formula (7-2) comprises a group represented by the formula (4) incorporated in any of Ra 3 , Ra 17 and Ra 18 , preferably Ra 3 .
  • the group represented by the formula (4) is more preferably represented by any of the formulae (6-1) to (6-3).
  • the sensitizing dye represented by the formula (1) is more preferably represented by the formula (7-1).
  • LP does not disconnect from E and discolor itself when irradiated with hologram recording light but disconnects from E and discolors itself when irradiated with light different from hologram recording light.
  • the hologram recording/reproducing method comprises effecting hologram recording with a sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5), and then irradiating entirely with light other than hologram recording light so that the compound represented by any of the formulae (1) and (3-1) to (3-5) is self-discolored and fixed, whereby reproduction can be effected by irradiating with the same light as hologram recording light without extinguishing recorded interference fringes developed by refractive index modulation.
  • the compounds represented by the following formulae (5-1) to (5-5) may be used for purposes other than hologram sensitizing dye, e.g., medicines, dyes, agricultural chemicals.
  • these compounds are preferably used as optically self-discolorable dye, more preferably optically self-discolorable sensitizing dye particularly for photon mode recording material to be dry-processed
  • these compounds are most preferably used as sensitizing dye for hologram recording material.
  • Za 1 to Za 8 , Ra 1 to Ra 6 , Ma 1 to Ma 21 , na 1 to na 6 , ka 1 to ka 5 , Cl and y are as defined in the formulae (3-1) to (3-5).
  • the sensitizing dye represented by the formula (5-1) comprises a group represented by any of the following formulae (6-1) to (6-3) incorporated in any of Ra 1 , Ra 2 and Ma 3 to Ma 5
  • the sensitizing dye represented by the formula (5-2) comprises a group represented any of the following formulae (6-1) to (6-3) incorporated in any of Ra 3 , Ma 10 and Ma 11
  • the sensitizing dye represented by the formula (5-3) comprises a group represented any of the following formulae (6-1) to (6-3) incorporated in any of Ma 12 to Ma 14
  • the sensitizing dye represented by the formula (5-4) comprises a group represented any of the following formulae (6-1) to (6-3) incorporated in any of Ra 4 , Ma 16 and Ma 17
  • the sensitizing dye represented by the formula (5-5) comprises a group represented any of the following formulae (6-1) to (6-3) incorporated in any of Ra 5 , Ra 6 , Ma 20 and Ma 21 .
  • the compounds represented by the formulae (5-1) to (5-5) of the invention each are preferably represented by any of the formulae (5-1), (5-2) and (5-4), more preferably the formula (5-1) or (5-2), even more preferably the formula (5-1).
  • the compounds represented by the formulae (5-1) to (5-5) of the invention each are preferably represented by the formula (7-1) or (7-2), more preferably the formula (7-1).
  • sensitizing dye for hologram recording material represented by the formula (1) of the invention the compound represented by the formulae (5-1) to (5-5), the discolorable dye of the invention, and the optically discolorable sensitizing dye of the invention will be given below, but the invention is not limited thereto.
  • a trimethine cyanine dye having a benzooxazole ring is particularly preferred.
  • a monomethine cyanine dye having a benzooxazole ring is particularly preferred.
  • a hologram recording method and hologram recording material of the invention will be further described hereinafter.
  • the hologram recording method of the invention preferably involves any of 1) polymerization reaction, 2) color development reaction, 3) latent image color development-coloring material self-sensitized amplification color development reaction, 4) latent image color development reaction-coloring material sensitizing polymerization reaction, 6) dye discoloration reaction and 7) remaining discolorable dye latent image-latent image sensitization polymerization reaction, preferably 2) color development reaction, 3) latent image color development-coloring material self-sensitized amplification color development reaction, 4) latent image color development reaction-coloring material sensitizing polymerization reaction, 6) dye discoloration reaction and 7) remaining discolorable dye latent image-latent image sensitization polymerization reaction, more preferably 2) color development reaction, 4) latent image color development reaction-coloring material sensitizing polymerization reaction, 6) dye discoloration reaction and 7) remaining discolorable dye latent image-latent image sensitization polymerization reaction, using a sensitizing dye represented by the formula (1) to record
  • the hologram recording material of the invention be not subjected to wet process after hologram exposure.
  • the hologram recording material of the invention is preferably not of rewritable type.
  • the term "not of rewritable type" as used herein is meant to indicate the type which causes irreversible reaction to perform recording. Once recorded, data can be stored without being rewritten even in an attempt to overwrite thereon.
  • the hologram recording material of the invention is suitable for the storage of important data which are needed to be stored over an extended period of time. It goes without saying that data can be additionally recorded on unrecorded area. In this sense, this type of a recording material is called "write-once-read-many type" recording material.
  • the light to be used in the hologram recording method of the invention is preferably any of ultraviolet ray, visible light and infrared ray having a wavelength of from 200 to 2,000 nm, more preferably ultraviolet ray or visible light having a wavelength of from 300 to 700 nm, even more preferably visible light having a wavelength of from 400 to 700 nm.
  • the radiation to be used in the hologram recording method of the invention is preferably coherent laser beam (having uniform phase and wavelength).
  • the laser to be used herein there may be used any of solid laser, semiconductor laser, gas laser and liquid laser.
  • Preferred examples of laser beam include YAG laser second harmonic having a wavelength of 532 nm, YAG laser third harmonic having a wavelength of 355 nm, semiconductor laser such as GaN laser or InGaN laser having a wavelength of from about 400 to 415 nm, semiconductor laser such as AlGaInP having a wavelength of about 650 nm to 660 nm, Ar ion laser having a wavelength of from 488 nm or 515 nm, He-Ne laser having a wavelength of 632 nm to 633 nm, Kr ion laser having a wavelength of 647 nm, ruby laser having a wavelength of 694 nm, and Ho-Cd laser having a wavelength of 636 nm, 634 nm, 5
  • pulse laser on the order of nanosecond or picosecond is preferably used.
  • YAG laser second harmonic having a wavelength of 532 nm or semiconductor laser such as GaN laser or InGaN laser having a wavelength of from about 400 to 415 nm and AlGaInP laser having a wavelength of from about 650 to 660 nm is preferably used.
  • the wavelength of the light for use in hologram reproduction is preferably the same as or longer than, more preferably the same as that of the light for use in hologram exposure (recording).
  • the hologram recording material which has been subjected to hologram exposure may be fixed by either or both of light and heat.
  • fixing is preferably effected only by light, particularly light having a wavelength range that can be absorbed by LP in the sensitizing dye represented by the formula (1).
  • the sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5) be discolored so that it can no longer absorb hologram reproducing light, making it possible to obtain a high absolute diffraction efficiency and allowing reproduction without destroying recorded data even when irradiated with light during reproduction.
  • the hologram recording material is entirely irradiated with ultraviolet ray or visible light (non-interference exposure).
  • Preferred examples of the light employable herein include visible light laser, ultraviolet laser, carbon arc, high voltage mercury vapor lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, LED, and organic EL.
  • fixing is preferably effect at a temperature of from 40°C to 160°C, more preferably from 60°C to 130°C.
  • light and heat fixing are effect, light and heat may be applied at the same time or separately.
  • the refractive index modulation during recording of interference fringes is preferably from 0.00001 to 0.5, more preferably from 0.0001 to 0.3. It is preferred that the more the thickness of the hologram recording material is, the less is the refractive index modulation. It is preferred that the less the thickness of the hologram recording material is, the more is the refractive index modulation.
  • the diffraction efficiency may range from 0% to 100%, preferably 30% or more, more preferably 60% or more, most preferably 80% or more.
  • the sensitivity of a hologram recording material is normally represented by exposure per unit area (mJ/cm 2 ). The less this value is, the higher is the sensitivity.
  • the exposure at which the sensitivity is defined differs from literature or patent to literature or patent. In some cases, the exposure at which recording (refractive index modulation) begins is defined as sensitivity. In other cases, the exposure at which the maximum diffraction efficiency (refractive index modulation) is given is defined as sensitivity. In further cases, the exposure at which half the maximum diffraction efficiency is given is defined as sensitivity. In still further cases, the exposure at which the gradient of diffraction efficiency relative to exposure E becomes maximum is defined as sensitivity.
  • the refractive index modulation ⁇ n at which a certain diffraction efficiency is given is inversely proportional to the thickness d.
  • the sensitivity at which a certain diffraction efficiency is given differs with thickness.
  • sensitivity is defined by "exposure at which half the maximum diffraction efficiency is given (mJ/cm 2 )".
  • the sensitivity of the hologram recording material of the invention is preferably 2 J/cm 2 or less, more preferably 1 J/cm 2 or less, even more preferably 500 mJ/cm 2 or less, most preferably 200 mJ/cm 2 or less if the thickness is from about 10 ⁇ m to 200 ⁇ m.
  • the hologram recording material of the invention is used in holographic memory as an optical recording medium
  • many two-dimensional digital data (referred to as "signal light") be recorded using a spatial light modulation element (SLM) such as DMD and LCD.
  • SLM spatial light modulation element
  • Recording is preferably accomplished by multiplexed recording to raise the recording density.
  • multiplexed recording methods include angular multiplexed, phase multiplexed, wavelength multiplexed and shift multiplexed recording methods. Preferred among these multiplexed recording methods are angular multiplexed recording and shift multiplexed recording.
  • CCD or CMOS is preferably used.
  • the hologram recording material of the invention is used in holographic memory as an optical recording medium, it is essential that multiplexed recording be effected to enhance the capacity (recording density).
  • multiplexed recording involving preferably 10 or more times, more preferably 50 times or more, most preferably 100 times or more of recording jobs is performed. More preferably, any multiplexed recording can be effected always at a constant exposure to simplify recording system and enhance S/N ratio.
  • the hologram recording material of the invention is preferably stored in a light-shielding cartridge during storage. It is also preferred that the hologram recording material be provided with a light filter capable of cutting part of wavelength range of ultraviolet ray, visible light and infrared ray other than recording light and reproduced light on the surface or back surface or on the both surfaces thereof.
  • the optical recording medium may be in the form of disc, card or tape or in any other form.
  • This recording process preferably involves the use of at least a sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5), a polymerization initiator, a polymerizable compound and a binder wherein the polymerizable compound and the binder have different refractive indexes and allows the sensitizing dye to absorb light to cause photopolymerization which makes the composition ratio of the polymerizable compound to the binder different from the bright interference area to the dark interference area, whereby the recording of an interference fringes by refractive index modulation is effected.
  • a sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5)
  • sensitizing dyes represented by the formulae (1) and (3-1) to (3-5) of the invention are discolored and fixed by irradiating with light in a specific wavelength range after hologram recording, recorded data cannot be destroyed nor absorbed even upon irradiation with hologram reproducing light, making it possible to obtain a high absolute diffraction efficiency.
  • the binder preferably has a refractive index different from that of the polymerizable compound.
  • the refractive index difference between the polymerizable compound and the binder in bulky form be great, more preferably 0.01 or more, even more preferably 0.05 or more, particularly 0.1 or more.
  • one of the polymerizable compound or the binder contain at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom and sulfur atom and the other be free of these groups or atoms.
  • Either the polymerizable compound or the binder may have a greater refractive index than the other.
  • polymerizable compound as used herein is meant to indicate a compound which can undergo addition polymerization with a radical, acid (Bronsted acid or Lewis acid) or base (Bronsted base or Lewis base) generated when the sensitizing dye (or coloring material) or polymerization initiator with light to form an oligomer or polymer.
  • the polymerizable compound of the invention may be monofunctional or polyfunedonal, may be of one-component system or multi-component system or may be a monomer, prepolymer (e.g., dimer, oligomer) or mixture thereof, preferably monomer.
  • the polymerizable compound may stay liquid or solid at room temperature but is preferably a liquid having a boiling point of 100°C or more or a mixture of a liquid monomer having a boiling point of 100°C or more and a solid monomer.
  • the polymerizable compound of the invention can be roughly divided into radical-polymerizable compound and cationically- or anioniocally-polymerizable compound.
  • radical-polymenzable compound and the cationically- or anioniocally- polymerizable compound will be described hereinafter in connection with the two groups: A) case where the refractive index of polymerizable compound is greater than that of binder and B) case where the refractive index of binder is greater than that of polymerizable compound.
  • the radical-polymerizable compound preferably has a high refractive index.
  • the high refractive index radical-polymerizable compound of the invention is preferably a compound having at least one ethylenically-unsaturated double bond per molecule and at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom or sulfur atom per molecule, more preferably a liquid having a boiling point of 100°C or more.
  • radical-polymerizable compound examples include the following monomers and prepolymers (dimer, oligomer) comprising these polymerizable monomers.
  • Preferred examples of the high refractive index radical-polymerizable monomer include styrene, 2-chlorostyrene, 2-bromostyrene, methoxystyrene, phenyl acrylate, p-chlorophenyl acrylate, 2-phenylethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, 2-(p-chlorophenoxy)ethyl acrylate, benzyl acrylate, 2-(I-naphthyloxy)ethyl acrylate, 2,2-di(p-hydroxyphenyl)propane diacrylate, 2,2-di(p-hydroxyphenyl)propane dimethacrylate, di(2-methacryloxyethyl)ether of bisphenol A, di(2-acryloxy ethyl)ether of bisphenol A, di(2-metbaayloxy)ether of tetrachloro-bisphenol A, di
  • the preferred polymerizable compound is a liquid but may be used in admixture with a second solid polymerizable compound such as N-vinylcarbazole, 2-naphthyl acrylate, pentachlorophenyl acryatc, 2,4,6-tribromophenyl acrylate, disphenol A diacrylate, 2-(2-naphthyloxy)ethyl and N-phenylmaleimide.
  • a second solid polymerizable compound such as N-vinylcarbazole, 2-naphthyl acrylate, pentachlorophenyl acryatc, 2,4,6-tribromophenyl acrylate, disphenol A diacrylate, 2-(2-naphthyloxy)ethyl and N-phenylmaleimide.
  • the radical-polymerizable compound preferably has a low refractive index.
  • the low refractive index radical-polymerizable compound of the invention preferably has at least one ethylenically-unsaturated double bond per molecule but is free of aryl, group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom and sulfur atom.
  • the radical-polymerizable compound of the invention is preferably a liquid having a boiling point of 100°C or more.
  • radical-polymerizable compound of the invention include the following polymerizable monomers and prepolymers (dimer, oligomer, etc.) comprising these polymerizable monomers.
  • Preferred examples of the low refractive index radical-polymerizable compound employable herein include t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 1,5-pentanediol diacrylate, ethylene glycol diacrylate, 1,4-butanediol diacrylate, diethylene glycol diacrylate, hexamethylene glycol diacrylate, 1,3-propanediol diacrylate, decamethylene glycol diacrylate, 1,4-cyclohexyldiol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, trimethylolpropane diacrylate, pentacrythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, 1,3-propanediol dimethacryl
  • 1,5-pentanediol dimethacrylate diallyl fumarate, 1H,1H-perflurooctyl acrylate, 1H,1H, 2H,2H-perfluorooctyl methacrylate. 1H,1H, 2H,2H-perfluorooctyl acrylate, and 1-vinyl-2-pyrrolidone.
  • More desirable among these low refractive index radical-polymerizable compounds are decanediol diacrylate, isobornyl acrylate, triethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diemethacrylate, ethoxyethoxy acrylate, triacrylate ester of ethoxylated trimethylopropane, and 1-vinyl-2-pyrrolidine.
  • Even more desirable among these low refractive index radical-polymerizable compounds are decanediol diacrylate, isobornyl acrylate, triethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diemethacrylate, ethoxyethoxy acrylate, 1H,1H-perflurooctyl acrylate, 1H,1H,2H,2H-perfluorooctyl methacrylate, 1H,1H, 2H,2H-perfluorooctyl acrylate, and 1-vinyl-2-pyrrolidone.
  • the preferred polymerizable compound is a liquid but may be used in admixture with a second solid polymerizable compound monomer such as N-vinylcaprolactam.
  • cationically-polymerizable compound as used herein is meant to indicate a compound which begins polymerization with an acid generated when the sensitizing dye and the cation polymerization initiator are irradiated with light.
  • anionically-polymerizable compound as used herein is meant to indicate a compound which begins polymerization with a base generated when the sensitizing dye and the anion polymerization initiator are irradiated with light.
  • the cationically-polymerizable compound of the invention is preferably a compound having at least one oxirane ring, oxethanone ring, vinylether group or N-vinylcarbazole moiety, more preferably N-vinylcarbazole moiety per molecule.
  • the anionically-polymerizable compound of the invention is preferably a compound having at least one oxirane ring, oxethanone ring, vinylether group, N-vinyl carbazole moiety, ethylenic double bond moiety provided with an electrophilic substituent, lactone moiety, lactam moiety, cyclic urethane moiety, cyclic urea moiety or cyclic siloxane moiety per molecule, more preferably oxiranc ring moiety.
  • the cationically- or anionically- polymerizable compound preferably has a high refractive index.
  • the high refractive index cadonically- or anionically-polymerizable compound of the invention is preferably a compound having at least one oxirane ring, oxethanone ring, vinylether group or N-vinylcarbazole moiety per molecule and at least aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom or sulfur atom per molecule, more preferably at least one aryl group.
  • the cationically- or anionically- polymerizable compound of the invention is preferably a liquid having a boiling point of 100°C or more.
  • cationically- or anionically-polymerizable compound of the invention include the following polymerizable monomers and prepolymers (dimer, oligomer, etc.) comprising these polymerizable monomers.
  • Preferred examples of the high refractive index cationically- or anionically-polymenzable monomers having oxirane ring include phenylglycidyl ether, phthalic acid diglycidyl ester, trimellitic acid triglycidyl ester, resorcine diglycidyl ether, dibromophenyl glycidyl ether, dibromoneopentyl glycol diglycidyl ether, 4,4'-bis(2,3-epoxypropoxyperfluoro isopropyl)diphenyl ether, p-bromostyrene oxide, bisphenol-A-diglycidyl ether, tetrabromobisphenol-A-diglycidyl ether, bisphenal-F-diglycidyl ether, and 1,3-bis(3',4'-epoxycyclohexyl)ethyl)-1,3,-diphenyl-1,3,-dimethyldisilox
  • high refractive index cation or anionically-polymerizable monomer having oxethanone ring include compounds obtained by replacing the oxirane ring in the specific examples of the high refractive index cation or anionically-polymerizable monomer having oxirane ring by oxethanone ring.
  • high refractive index cationically- or anionically-polymerizable monomer having vinylether group moiety examples include vinyl-2-chloroethyl ether, 4-vinyletherstyrene, hydroquinone divinyl ether, phenylvinyl ether, bisphenol A divinyl ether, tetrabromobisphenol A divinyl ether, bisphenol F divinyl ether, phenoxyethylenevinyl ether, and p-bromophenoxycthylenevinyl ether.
  • high refractive index cationically-polymerizable monomer examples include styrene-based monomers such as styrene, 2-chlorostyrene, 2-bromostyrene and methoxystyrene and N-vinylcarbazole.
  • the cationically- or anionically- polymerizable compound preferably has a low refractive index.
  • the low refractive index cationically- or anionically-polymerizable compound of the invention is preferably a compound having at least one oxirane ring, oxethanone ring, vinylether group or N-vinylcarbazole moiety per molecule but free of aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom and sulfur atom.
  • the cationically- or anionically-polymerizable compound of the invention is preferably a liquid having a boiling point of 100°C or more.
  • cationically- or anionically-polymerizable compound of the invention include the following polymerizable monomers and prepolymers (dimer, oligomer, etc.) comprising these polymerizable monomers.
  • the low refractive index cationically- or anionically-polymerizable monomer having oxirane ring include glyceroldiglycidyl ether, glyceroltriglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropanctriglycidyl ether, 1,6-hexanediolglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, adipic acid diglycidyl ester, 1,2,7,8-dicpoxyoctane, 1,6-dimethylolperfluorohexane diglycidyl ether, vinyl cyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclo
  • the low refractive index cationically- or anionically-polymerizable monomer having oxathanone ring include compounds obtained by replacing the oxirane ring in the aforementioned specific examples of low refractive index cationically- or anionically-polymerizable monomer having oxirane ring by oxethanone ring.
  • the low refractive index cationically- or anionically-polymerizable monomer having vinylether group moiety examples include vinyl-n-butylether, vinyl-t-butylether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, propylene glycol divinyl ether, neopentyl glycol divinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, trietbylene glycol divinyl ether, trimethylol propane monovinyl ether, trimethylol propane divinyl ether, trimethylol propane trivinyl ether, allyl vinyl ether, 2,2-bis(4-cyclohexanol)propanol divinyl ether, and 2,2-bis(4-cyclohexanol)trifluoropropane divinyl ether.
  • binder to be used in recording of interference fringes by polymerization reaction will be described hereinafter in connection with the two groups: A) case where the refractive index of polymerizable compound is greater than that of binder and B) case where the refractive index of binder is greater than that of polymerizable compound.
  • binder having a smaller refractive index than polymerizable compound A) Preferred examples of binder having a smaller refractive index than polymerizable compound
  • the binder preferably has a low refractive index.
  • the binder of the invention is preferably a binder free of aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom and sulfur atom.
  • the low refractive index binder include acrylates, ⁇ -alkyl acrylates, acidic polymers, interpolymers (e.g., polymethacrylic acid methyl, polymethacrylic acid ethyl, copolymer of methyl methacylate with other (meth)acrylic acid akylesters), polyvinylesters (e.g., polyvinyl acetate, polyacetic acid/acrylic acid vinyl, polyacetic acid/methacrylic acid vinyl, hydrolyzable polyvinyl acetate), ethylene/vinyl acetate copolymers, saturated and unsaturated polyurethanes, butadiene polymers and copolymers, isoprene polymers and copolymers, high molecular polyethylene oxides of polyglycol having an average molecular weight of from about 4,000 to 1,000,000, epoxy compounds (e.g., epoxylated compounds having acrylate or methacrylate), polyamides (e.g., N-me
  • the low refractive index binder include fluorine atom-containing polymers.
  • a preferred example of the fluorine atom-containing polymers is an organic solvent-soluble polymer comprising a fluoroolefin as an essential component and one or more unsaturated monomers selected from the group consisting of alkylvinyl ether, alicyclic vinyl ether, hydroxyvinyl ether, olefin, haloolefin, unsaturated carboxylic acid, ester thereof and carboxylic acid vinyl ester as copolymerizable components.
  • the fluorine atom-containing polymer preferably has a weight-average molecular weight of from 5,000 to 200,000 and a fluorine atom content of from 5 to 70% by weight.
  • fluorine atom-containing polymer examples include Lumiflon Series (e.g., Lumiflon LF200; weight-average molecular weight: approx. 50,000, produced by Asahi Glass Co., Ltd.), which are organic solveat-soluble fluorine atom-containing polymers having hydroxyl group.
  • Lumiflon Series e.g., Lumiflon LF200; weight-average molecular weight: approx. 50,000, produced by Asahi Glass Co., Ltd.
  • organic solvent-soluble fluorine atom-containing polymers have been marketed by DAIKIN INDUSTRIES, LTD., Central Glass Co., Ltd., Penwalt Corp., etc. These products, too, can be used.
  • fluorine atom-containing polymer examples include silicon compounds such as pioly(dimethylsiloxane) and silicon oil free of aromatic group.
  • epoxy oligomer compounds free of aromatic groups can be used as low refractive index reactive binders.
  • the binder preferably has a high refractive index.
  • the binder of the invention is preferably a binder containing at least one aryl group, aromatic heterocyclic group, chlorine atom, bromine atom, iodine atom or sulfur atom, more preferably aryl group.
  • the high refractive index binder include polystyrene polymers, acrylonitrile, maleic anhydride, acrylic acid, methacrylic acid, methacrylic acid ester copolymer, vinylidene chloride copolymer (e.g., vinylidene chloride/acrylonitrile copolymer, vinylidene chloride/methacrylate copolymer, vinylidene/vinyl acetate copolymer), polyvinyl chloride copolymer (e.g., polyvinyl chloride/acetate, vinyl chloride/acrylonitrile copolymer), polyvinyl benzal synthetic rubber (e.g., butadiene/acrylonitrile copolymer, acrylonitrile/butadiene/styrene copolymer, methacrylate/acrylonitrile/butadiene/styrene copolymer, 2-chlorobutadiene-1,3-polymer, chlorinated rubber,
  • high refractive index binder examples include silicon compounds such as poly (methylphenylsiloxane) and 1,3,5 trimethyl-1,1,3,5,5-pentaphenyltrisiloxane and silicon oil containing much aromatic groups.
  • epoxy oligomer compounds containing much aromatic groups can be used as high refractive index reactive binder.
  • Preferred examples of the polymerization initiator to be used interference fringes recording involving polymerization reaction of the invention include ketone-based, organic peroxide-based, trihalomethyl-substituted triazine-based, diazonium salt-based, diaryl iodonium salt-based, sulfonium salt-based, borate-based, diaryl iodonium-organic boron complex-based, sulfonium-organic boron complex-based, cationic sensitizing dye-organic boron complex-based, anionic sensitizing dye-onium salt complex-based, metal-allene complex-based and sulfonic acid ester-based radical polymerization initiators (radical generators), cationic polymerization initiators (acid generators) and radical polymerization-cationic polymerization initiators.
  • an acid proliferator is preferably used to enhance sensitivity.
  • Preferred examples of the acid proliferator employable herein include those exemplified in Japanese Patent Application No. 2003-182849.
  • an anionic polymerization initiator and a base generator is preferably used.
  • a base proliferator is preferably used to enhance sensitivity.
  • Specific preferred examples of the anionic polymerization initiator and base proliferator include those exemplified in Japanese Patent Application No. 2003-178083.
  • polymerization initiator examples include those exemplified in Japanese Patent Application No. 2004-238392.
  • color development reaction as used herein is meant to indicate a reaction involving the change of absorption spectrum form or preferably either or both of the shift of ⁇ max to longer wavelength and rise of ⁇ in absorption spectrum in the range of ultraviolet ray, visible light and infrared ray having a wavelength of from 200 mn to 2,000 nm.
  • the color development reaction preferably occurs at a wavelength of from 200 nm to 1,000 nm, more preferably from 300 nm to 900 nm
  • the hologram recording material of the invention preferably contains at least:
  • sensitizing dyes represented by the formulae (1) and (3-1) to (3-5) of the invention are discolored and fixed by irradiating with light in a specific wavelength range after hologram recording, recorded data cannot be destroyed nor absorbed even upon irradiation with hologram reproducing light, making it possible to obtain a high absolute diffraction efficiency.
  • the refractive index of the dye rises in the range of from close to linear absorption maxima wavelength ( ⁇ max) to wavelength longer than linear absorption maxima wavelength ( ⁇ max), rises drastically in the range of from ⁇ max to wavelength about 200 nm longer than ⁇ max. In this wavelength range, some dyes show a refractive index of more than 1.8, as high as more than 2 in some cases. On the other hand, organic compounds which are not a dye, such as binder polymer, normally have a refractive index of from about 1.4 to 1.6.
  • the refractive index of the dye formed by the recording component preferably reaches maximum in the vicinity of laser wavelength at which reproduction is effected.
  • Preferred examples of the sensitizing dye include those exemplified above.
  • interference fringe-recording component includes the following combinations. Specific preferred examples of these combinations include those described in Japanese Patent Application No. 2004-238077.
  • a binder polymer is incorporated in the compound.
  • Preferred examples of the binder polymer include those exemplified above with reference to (1) polymerization reaction and those disclosed in Japanese Patent Application No. 2004-238077.
  • This hologram recording method comprises at least a first step of forming a coloring material having no absorption at hologram reproducing light wavelength as a latent image by hologram exposure and a second step of irradiating the coloring material latent image with light having a wavelength different from hologram exposure wavelength, at which the sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5) exhibits a molar absorption coefficient of 5,000 or less to cause the self-sensitized amplification of the coloring material, whereby an interference fringes is recorded as refractive index modulation, which steps being effected in a dry process.
  • This hologram recording method is advantageous in high speed writing properties, high S/N ratio reproducibility, etc.
  • magnification or 2 or more is preferably effected at the second step
  • more preferably one fifth even more preferably one tenth, most preferably one thirtieth (that is, magnification of 5 or more, more preferably 10 or more, most preferably 30 or more is effected at the second step).
  • the second step preferably involves the irradiation with light or both of the irradiation with light and the application of heat, more preferably the irradiation with light.
  • the irradiation with light preferably involves entire exposure (so-called solid exposure, blanket exposure or non-imagewise exposure).
  • Preferred examples of the light source to be used herein include visible light laser, ultraviolet laser, infrared laser, carbon are, high voltage mercury vapor lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, LED, and organic EL.
  • a sharp cut filter, band pass filter, diffraction grating or the like is preferably used as necessary.
  • the sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5) of the invention be discolored and fixed at the same time with the other compounds.
  • the sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5) of the invention be discolored and fixed at the same time with the other compounds.
  • the hologram recording material allowing the aforementioned hologram recording method preferably comprises at least:
  • This hologram recording method preferably comprises a first step at which the sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5) having absorption at hologram exposure wavelength absorbs light during hologram exposure to generate excited state with the energy of which it then discolors the discolomble dye having a molar absorption coefficient of 1,000 or less, preferably 100 or less, most preferably 0 at hologram reproducing light wavelength, whereby the discolorable dye left undiscolored forms a latent image and a second step at which the latent image of discolorable dye left undiscolored is irradiated with light having a wavelength different from that used for hologram exposure to cause polymerization by which an interference fringes is recorded as refractive index modulation.
  • This hologram recording method is excellent in high speed recording properties, adaptability to multiplexed recording, storage properties after recording, etc.
  • This hologram recording method more preferably comprises a first step at which the sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5) having absorption at hologram exposure wavelength absorbs light during hologram exposure to generate excited state in which it then undergoes energy movement or electron movement with the discoloring agent precursor as defined in Clause 6) to cause the discoloring agent precursor to generate a discoloring agent which then discolors the discolorable dye whereby the discolorable dye left undiscolored forms a latent image and a second step at which the latent image of discolorable dye left undiscolored is irradiated with light having a wavelength different from that used for hologram exposure to cause energy movement or electron movement by which a polymerization initiator is activated to cause polymerization by which an interference fringes is recorded as refractive index modulation.
  • the sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5) of the invention be discolored and fixed at the same time with the other compounds.
  • the sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5) of the invention be discolored and fixed at the same time with the other compounds.
  • the compound group allowing the aforementioned hologram recording method preferably comprises at least:
  • the compound group preferably further contains 6) a discoloring agent precursor capable of undergoing electron or energy movement from excited state of sensitizing dye to generate a discoloring agent at the first step.
  • Preferred examples of the polymerization initiator, the polymerizable compound and the binder include those exemplified with reference to 1) polymerization reaction.
  • the light emitted at the second step preferably has a wavelength range at which the sensitizing dye represented by any of the formulae (1) and (3-1) to (3-5) exhibits a molar absorption coefficient of 1,000 or less, more preferably 500 or less.
  • the discolorable dye preferably exhibits a molar absorption coefficient of 1,000 or more.
  • discoloring agent precursor and the polymerization initiator partly or wholly act as each other.
  • the sensitizing dyc can perform electron movement sensitization only on the discoloring agent precursor and the polymerization initiator can perform electron movement sensitization only by the discolorable dye.
  • the remaining discolorable dye be decomposed and fixed at the second step or the subsequent fixing step involving either or both of irradiation with light and application of heat.
  • the hologram recording material is irradiated with YAG ⁇ SHG laser beam having a wavelength of 532 nm so that the laser beam is absorbed by the sensitizing dye to generate excited state. Energy or electron is then moved from the excited state of sensitizing dye to the discoloring agent precursor to generate a discoloring agent by which the discolorable dye is then discolored. As a result, a latent image can be formed by the remaining discolorable dye (first step). Subsequently, the hologram recording material is irradiated with light having a wavelength of from 350 nm to 420 nm so that the light is absorbed by the remaining discolorable dye.
  • the polymerizable compound when the polymerizable compound has a smaller refractive index than the binder, the polymerizable compound gathers at the polymerization area, causing the drop of refractive index (second step).
  • the polymerizable compound gathers at the polymerization area, causing the drop of refractive index (second step).
  • the proportion of binder is higher in the bright interference area.
  • the refractive index modulation can be recorded as interference fringes. So far as the sensitizing dye and remaining discolorable dye can be decomposed and discolored at the first and second steps or the subsequent fixing step, a hologram recording material excellent in non-destructive reproduction, storage properties and diffraction efficiency can be provided.
  • the hologram recording material having data, image, etc. recorded thereon is again irradiated with a laser beam having a wavelength of 532 nm, the data, image, etc. can be reproduced.
  • the hologram recording material of the invention can act as a desired optical material.
  • discolorable dye latent image-latent image sensitized polymerization reaction examples include those exemplified in Japanese Patent Application No. 2004-88790.
  • the hologram recording material of the invention may further comprise additives such as electron-donating compound, electron-accepting compound, chain transfer agent, crosslinking agent, heat stabilizer, plasticizer and solvent incorporated therein besides the aforementioned sensitizing dyes represented by the formulae (1) and (3-1) to (3-5), interference fringe-recording component, polymerization initiator, polymerizable compound, binder, discolorable dye, discoloring agent precursor, etc. as necessary.
  • additives such as electron-donating compound, electron-accepting compound, chain transfer agent, crosslinking agent, heat stabilizer, plasticizer and solvent incorporated therein besides the aforementioned sensitizing dyes represented by the formulae (1) and (3-1) to (3-5), interference fringe-recording component, polymerization initiator, polymerizable compound, binder, discolorable dye, discoloring agent precursor, etc. as necessary.
  • the electron-donating compound is capable of reducing the radical cation in the sensitizing dyes represented by the formulae (1) and (3-1) to (3-5), coloring materials or discolorable dyes.
  • the electron-accepting compound is capable of oxidizing the radical anion in the sensitizing dyes represented by the formulae (1) and (3-1) to (3-5), coloring materials or discolorable dyes.
  • both the electron-donating compound and the electron-accepting compound are capable of reproducing the sensitizing dye.
  • Specific preferred examples of these compounds include those exemplified in Japanese Patent Application No. 2004-238077.
  • the electron-donating compound is useful for the enhancement of sensitivity because it can rapidly reproduce from the radical cation of the sensitizing dyes represented by the formulae (1) and (3-1) to (3-5), coloring materials or discolorable dye produced by the movement of electron to the dye precursor group.
  • the electron-donating compound there is preferably used one having a more negative oxidation potential than sensitizing dye, coloring material and discolorable dye. Specific preferred examples of the electron-donating compound will be given below, but the invention is not limited thereto.
  • the electron-donating compound include phenothiazine-based compounds (e.g., 10-methylphenothiazine, 10-(4'-methoxyphenyl) phenothiazine), triphenylamine-based compounds (e.g., triphenylamine, tri(4'-methoxyphenyl)amine), and TPD-based compounds (e.g., TPD). More desirable among these electron-donating compounds arc phenothiazine-based compounds. Most desirable among these electron-donating compounds is N-methylphenothtazine.
  • the sensitizing dye, acid generator, base generator, dye precursor, discolorable dye, discoloring agent precursor, electron-donating compound and other components described above may be in the form of oligomer or polymer. These oligomers or polymers may be incorporated in the main chain or side chain. These components may be also in the form of copolymer.
  • the polymer chain may have any structure.
  • Preferred examples of the structure of the polymer chain include polyethers such as polyacrylate, polymethactylate, polystyrene and polyethylene oxide, polyesters, and polyamides.
  • the number of repeating units constituting the polymer or oligomer is from not smaller than 2 to not greater than 1,000,000, preferably from not smaller than 3 to not greater than 1,000,000, more preferably from not smaller than 5 to not greater than 500,000, even more preferably from not smaller than 10 to not greater than 100,000.
  • the molecular weight of the polymer or oligomer is preferably from not smaller than 500 to not greater than 10,000,000, more preferably from not smaller than 1,000 to not greater than 5,000,000, even more preferably from not smaller than 2,000 to not greater than 1,000,000, most preferably from not smaller than 3,000 to not greater than 1,000,000.
  • chain transfer agent examples include those exemplified in Japanese Patent Application No. 2004-238392.
  • Preferred examples of the chain transfer agent include thiols.
  • these thiols include 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 2-mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol, p-bromobenzenethiol, thiocyanuric acid, 1,4-bis(mercapto)benzene, and p-toluenethiol.
  • a chain transfer agent is preferably used.
  • the hologram recording material of the invention may comprise a heat stabilizer incorporated therein to enhance the storage properties thereof during storage.
  • useful heat stabilizers include hydroquinone, phenidonc, p-methoxypheno, alkyl-substituted hydroquinone, alkyl-substituted quinone, aryl-substituted hydroquinone, aryl-substituted quinone, catechol, t-butylcatechol, pyrogallol, 2-naphthol, 2,6-di-t-butyl-p-cresol, phenothiazine, and chloranyl.
  • the plasticizer is used to change the adhesivity, flexibility, hardness and other mechanical properties of the hologram recording material.
  • examples of the plasticizer employable herein include triethylene glycol dicaprylate, triethylene glycol bis(2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl sberate, tris(2-ethylhexyl) phosphate, tricresyl phosphate, dibutyl phthalate, alcohols, and phenols.
  • the hologram recording material of the invention may be prepared by any ordinary method.
  • the aforementioned binder and various components may be spread over the substrate in the form of solution in a solvent or the like using a spin coater, bar coater or the like.
  • ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, acetone and cyclohexanone
  • ester-based solvents such as ethyl acetate, butyl acetate, ethylene glycol diacetate, ethyl lactate and cellosolve acetate
  • hydrocarbon-based solvents such as tetrahydrofurane, dioxane and diethyl ether
  • cellosolve-based solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and dimethyl cellosolve
  • alcohol-based solvents such as methanol, ethanol, n-propanol, 2-propanol, n-butanol and diacetone alcohol
  • fluorine-based solvents such as 2,2,3,3-tetrafluoropropanol
  • halogenated hydrocarbon-based solvents such as dichloroxano
  • the hologram recording material of the invention can be prepared by spreading the aforementioned coating solution directly over the substrate using a spin coater, roll coater, bar coater or the like or by casting the coating solution into a film which is then laminated on the substrate using an ordinary method.
  • substrate as used herein is meant to indicate an arbitrary natural or synthetic support, preferably one which can occur in the form of flexible or rigid film, sheet or plate.
  • Preferred examples of the substrate include polyethylene terephthalate, resin-undercoated polyethylne terephthalate, flame- or electrostatically discharged polyethylene terephthalate, cellulose acetate, polycarbonate, polymethyl methacrylate, polyester, polyvinyl alcohol, and glass.
  • the solvent used can be evaporated away during drying.
  • the evaporation may be effected under heating or reduced pressure.
  • the film of the hologram recording material of the invention may be prepared by melting the binder comprising various components at a temperature of not lower than the glass transition temperature or melting point of the binder, and then melt-extruding or injection-molding the molten binder.
  • a reactive crosslinkable binder may be used as the binder so that the binder thus extruded or molded can be crosslinked and cured to raise the strength of the film.
  • the crosslinking reaction may involve radical polymerization reaction, cationic polymerization reaction, condensation polymerization reaction, addition polymerization reaction or the like.
  • methods disclosed in JP-A-2000-250382, JP-A-2000-172154, etc. are preferably used.
  • a method which comprises dissolving various components in a monomer solution for forming a binder, and than subjecting the monomer to photopolymerization or photopolymerization to produce a polymer which is then used as a binder.
  • the polymerization method employable herein include radical polymerization reaction, cationic polymerization reaction, condensation polymerization reaction, and addition polymerization reaction.
  • a protective layer for blocking oxygen may be formed on the hologram recording material.
  • the protective layer may be formed by laminating a film or sheet of a plastic such as polyolefin (e.g., polypropylene, polyethylene), polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyethylene terephthalate and cellophane on the hologram recording material using an electrostatic contact method or an extrusion machine or by spreading the aforementioned polymer solution over the hologram recording material.
  • a glass sheet may be laminated on the hologram recording material.
  • an adhesive or liquid material may be provided interposed between the protective layer and the photosensitive layer and/or between the substrate and the photosensitive layer to enhance airtightness.
  • the hologram recording material of the invention is used for holographic light memory, it is preferred from the standpoint of enhancement of S/N ratio during the reproduction of signal that the hologram recording material undergo no shrinkage after hologram recording.
  • the hologram recording material of the invention comprise an inflating agent disclosed in JP-A-2000-86914 incorporated therein or a shrinkage-resistant binder disclosed in JP-A-200-250382, JP-A-2000-172154 and JP-A-11-344917 incorporated therein.
  • the interference fringes gap be adjusted using a diffusion element disclosed in JP-A-3-46687, JP-A-5-204288, JP-T-9-506441, etc.
  • any multiplexed recording can be conducted at a constant exposure, i.e., with a linear rise of refractive index modulation relative to exposure. Therefore, a broad dynamic range can be obtained.
  • 2) to 4) and 6) and 7) process recording methods of the invention are very advantageous from the standpoint of the aforementioned adaptability to multiplexed recording.
  • the hologram recording material of the invention gives drastic solution to the aforementioned problems.
  • the hologram recording material of the invention allows quite a new recording method which attains high sensitivity, good storage properties, dry processing properties and multiplexed recording properties (high recording density).
  • the hologram recording material is particularly suited for optical recording medium (holographic optical memory).
  • the sensitizing dye when optically discolored and fixed after hologram recording, no deterioration can occur even upon irradiation with reproducing light after recording. In other words, non-destructive reproduction can be made, providing excellent storage properties. Further, when fixing is effected after recording, no absorption of hologram reproducing light can occur, making it possible to obtain a high absolute diffraction efficiency.
  • the hologram recording material of the invention can be used as three-dimensional display hologram, holographic optical element (HOE, such as headup display (HUD) for automobile, pickup lens for optical disc, head mount display, color filter for liquid crystal, reflector for reflective liquid crystal, lens, diffraction grating, interference filter, connector for optical fiber, light polarizer for facsimile, window glass for building), cover paper for book, magazine, and display for POP, etc.
  • HOE holographic optical element
  • the hologram recording material of the invention is preferably used for gift and credit card, paper money and packaging for the purpose of security against forgery.
  • the product was concentrated, subjected to decantation with ethyl acetate five times, purified through silica gel chromatography (developing solvent: 10 : 1 mixture of methylene and methanol), and then dissolved in methanol. 5.21 g (32 mmol) of ammonium hexafluorophosphate was then dissolved in the solution. The resulting crystal was withdrawn by filtration, washed with methanol, and then recrystallized from chloroform to obtain 1.36 g (yield: 4.5%) of an orange crystal of the desired compound S-1.
  • the structure of the product was identified by NMR and MS spectrosropy.
  • Example 1 of JP-A-6-43634 1.20% by weight of a radical polymerization initiator I-2, 1.80% by weight of a chain transfer agent MBO, 46.5% by weight of POEA as a monomer and 50.5% by weight of cellulose acetate butylate CAB 531-1 as a binder were used.
  • a known sensitizing dye DEAW described in JP-A-6-43634, and the inventive sensitizing dyes S-1 and S-7 were then used in an amount of 0.069% by weight, 1.00% by weight and 0.54% by weight, respectively, based on the solid content of the aforementioned mixture.
  • Comparative Sample 1 of composition for hologram recording material and Inventive Samples 11 and 12 were each spread (optionally in a multi-layer form) over a glass substrate to a thickness of about 100 ⁇ m using a blade to form a photosensitive layer which was then dried at room temperature in vacuo for 1 day to remove the solvent. The photosensitive layer was then covered by TAC layer to prepare a comparative hologram recording material 1 and inventive hologram recording materials 11 and 12.
  • the hologram recording materials were each then exposed to YAG laser second harmonic (532 nm; output: 2W) as a light source in a two-flux optical system for transmission hologram recording shown in Fig. 1 to perform recording.
  • the angle of the object light with respect to the reference light was 30 degrees.
  • the light had a diameter of 0.6 cm and an intensity of 8 mW/cm 2 .
  • the holographic exposure time was varied from 0.1 to 200 seconds (radiation energy ranging from 0.8 to 1,600 mJ/cm 2 ).
  • He-Ne laser beam having a wavelength of 632 nm was passed through the center of exposed area at the Bragg angle.
  • the ratio of diffracted light to incident light was then measured at real time. When a maximum diffraction efficiency was given, exposure was then suspended. Since the sensitizing dye shows no absorption at 632 nm, the hologram recording material is not sensitive to He-Ne laser beam.
  • the hologram recording materials were each then entirely irradiated with ultraviolet rays to visible light having a wavelength range of from 300 to 410 nm from a xenon lamp through a band pass filter so that the sensitizing dye was optically self-discolored to undergo fixation. Also during fixation, a He-No laser beam having a wavelength of 632 nm was passed through the center of the exposed area at the Bragg angle. The ratio of diffracted light to incident light (absolute diffraction efficiency) was measured at real time.
  • the hologram recording materials were each irradiated with reproducing light which is the same as the reference light having a wavelength of 532 nm used during recording.
  • the ratio of diffracted light to incident light was then measured.
  • the inventive hologram recording materials 11 and 12 exhibit a higher sensitivity than Comparative Example 1. It is thus made obvious that the inventive sensitizing dye can provide a hologram recording material having a higher sensitivity than known sensitizing dyes in the polymerization process (photopolymer process).
  • Comparative Example 1 which is known in JP-A-6-43634, exhibits a high absolute diffraction efficiency at 632 nm but exhibits a low absolute diffraction efficiency at 532 nm because the sensitizing dye cannot be fully decomposed and the remaining sensitizing dye absorbs reproducing light.
  • the inventive hologram recording materials 11 and 12 can be further optically self-discolored at the fixing step and thus exhibit no absorption at 532 nm.
  • the inventive hologram recording materials 11 and 12 give a high absolute diffraction efficiency at 632 nm as well as at 532 nm to advantage.
  • inventive hologram recording materials 11 and 12 When irradiated with light having a wavelength of 532 nm as reproducing light for 10 hours, the inventive hologram recording materials 11 and 12 showed no drop of diffraction efficiency. After one month of storage at room temperature, the inventive hologram recording materials 11 and 12 were each then measured for diffraction efficiency. These inventive hologram recording materials showed no special drop of diffraction efficiency.
  • the sensitizing dye, electron-donating compound, interference Binge-recording component, additives and binder PMMA-EA (poly(methyl methacrylate)-5% ethyl acrylate) copolymer; Mw: 101,000) set forth in Table 2 were dissolved in a double to quadruple amount of methylene chloride (optionally acetone or acetonitrile as well) under a red light to prepare hologram recording materials 101 to 107.
  • the term "%" as used herein is meant to indicate % by weight based on binder PMMA-EA.
  • compositions 101 to 107 for hologram recording material were each spread (optionally in a multi-layer form) over a glass substrate to a thickness of about 80 ⁇ m using a blade to form a photosensitive layer which was then dried at room temperature in vacuo for 1 day to remove the solvent.
  • the photosensitive layer was then covered by TAC layer to prepare hologram recording materials 101 to 107.
  • the hologram recording materials were each then exposed to YAG laser second harmonic (532 nm; output: 2W) as a light source in a two-flux optical system for transmission hologram recording shown in Fig. 1 to perform recording.
  • the angle of the object light with respect to the reference light was 30 degrees.
  • the light had a diameter of 0.6 cm and an intensity of 8 mW/cm 2 .
  • the holographic exposure time was varied from 0.1 to 400 seconds (radiation energy ranging from 0.8 to 1,600 mJ/cm 2 ).
  • He-Ne laser beam having a wavelength of 632 nm was passed through the center of exposed area at the Bragg angle.
  • the ratio of diffracted light to incident light was then measured at real time. When a maximum diffraction efficiency was given, exposure was then suspended. Since the sensitizing dye shows no absorption at 632 nm, the hologram recording material is not sensitive to He-Ne laser beam.
  • the hologram recording materials were each then entirely irradiated with ultraviolet rays to visible light having a wavelength range of from 300 to 410 mn from a xenon lamp through a band pass filter so that the sensitizing dye was optically self-discolored to undergo fixation. Also during fixation, a He-Ne laser beam having a wavelength of 632 nm was passed through the center of the exposed area at the Bragg angle. The ratio of diffracted light to incident light (absolute diffraction efficiency) was measured at real time.
  • the hologram recording materials were each irradiated with reproducing light which is the same as the reference light having a wavelength of 532 nm used during recording.
  • the ratio of diffracted light to incident light was then measured.
  • the comparative example which is known in JP-A-6-43634, exhibits a high absolute diffraction efficiency at 632 nm but shows a shrinkage as great as more than 5% during recording because it employs a photopolymer process involving radical polymerization.
  • the comparative example shows an extremely deteriorated S/N ratio when used as holographic memory. Thus, the comparative example is not suitable for this purpose.
  • the comparative example exhibits a low absolute diffraction efficiency at 532 because the sensitizing dye cannot be fully decomposed and the remaining sensitizing dye absorbs reproducing light.
  • the inventive hologram recording materials 101 to 107 employ a recording process which is quite different from the known hologram recording process, i.e., hologram recording process involving refractive index modulation by discoloration reaction rather than by the movement and polymerization of material.
  • the inventive hologram recording materials 101 to 107 can perform recording at a shrinkage as extremely small as 0.01% or less and thus are suitable particularly for holographic memory.
  • the inventive hologram recording materials 101 to 107 can be optically self-discolored at the fixing step and thus exhibit no absorption at 532 nm.
  • the inventive hologram recording materials 101 to 107 give a high absolute diffraction efficiency at 632 mn as well as at 532 nm to advantage.
  • the inventive hologram recording materials 101 to 107 showed no drop of diffraction efficiency.
  • inventive hologram recording materials show a substantially linear rise of An (calculated from modulation of refractive index in interference fringes, diffraction efficiency and layer thickness on the basis of Kugelnick's equation) with exposure (mJ/cm 2 ) and thus are advantageous in multiplexed recording.
  • the known photopolymer process hologram recording material as disclosed in JP-A-6-43634 was found to require more radiation dose in the latter stage of multiplexed recording than in the initial stage of multiplexed recording to perform the same recording because the polymerization of photopolymer has proceeded such that the rate of movement of monomer required for recording is reduced.
  • the known photopolymer process hologram recording material leaves something to be desired in the enhancement of multiplexiry, i.e., recording density.
  • sensitizing dye, electron-donating compound, dye precursor group + polymerization initiator, polymmizable compound and binder set forth in Table 4 were dissolved in a double to quintuple amount of methylene chloride (optionally acetone, acetonitrile or methanol in a small portion as well) under a red light to prepare hologram recording materials 201 to 204.
  • methylene chloride optionally acetone, acetonitrile or methanol in a small portion as well
  • the hologram recording material compositions 201 to 204 were each spread (optionally in a multi-layer form) over a glass substrate to a thickness of about 80 ⁇ m using a blade to form a photosensitive layer which was then dried at room temperature in vacuo for 1 day to remove the solvent.
  • the photosensitive layer was then covered by TAC layer to prepare hologram recording materials 201 to 204.
  • the hologram recording materials were each then exposed to YAG laser second harmonic (532 nm; output: 2W) as a light source in a two-flux optical system for transmission hologram recording shown in Fig. 1 to perform recording.
  • the angle of the object light with respect to the reference light was 30 degrees.
  • the light had a diameter of 0.6 cm and an intensity of 8 mW/cm 2 .
  • the holographic exposure time was varied from 0.1 to 40 seconds (radiation energy ranging from 0.8 to 320 mJ/cm 2 ) (first step).
  • He-Ne laser beam having a wavelength of 632 nm was passed through the center of exposed area at the Bragg angle.
  • the ratio of diffracted light to incident light was then measured at real time (diffraction efficiency ⁇ after first step).
  • the hologram recording material is not sensitive to He-Ne laser beam.
  • the hologram recording materials were each then entirely irradiated with light rays having a wavelength range of from 300 to 410 nm from a xenon lamp through a band pass filter (second step).
  • the absolute diffraction efficiency was measured at 632 run and 532 nm (diffraction efficiency ⁇ after second step).
  • the radiation dose required at the first step can be reduced to one seventh to one fifth of that required when the second step is not employed
  • the second step allows block exposure and hence polymerization with the discolorable dye left undiscolored at the first step as a latent image, resulting in amplification of refractive index modulation that allows the reduction of the first step, i.e., enhancement of sensitivity.
  • the known hologram recording material disclosed in JP-A-6-43634 cannot undergo such amplification that allows enhancement of sensitivity.
  • the inventive hologram recording material shows no absorption at 532 nm and thus gives a high absolute diffraction efficiency at 632 nm as well as at 532 nm.
  • inventive hologram recording materials 201 to 204 When irradiated with light having a wavelength of 532 nm as reproducing light for 10 hours, the inventive hologram recording materials 201 to 204 showed no drop of diffraction efficiency. After one month of storage at room temperature, the inventive hologram recording materials 201 to 204 were each then measured for diffraction efficiency. As a result, these inventive hologram recording materials showed no special drop of diffraction efficiency.
  • the hologram recording material of the invention shows a substantially linear rise of An (refractive index modulation in interference fringes, calculated from diffraction efficiency and layer thickness by Kugelnick's equation) with exposure (mJ/cm 2 ) both after the first and second steps and thus is favorable for multiplexed recording.
  • Multiplexed hologram recording was actually made on the same area of a hologram recording material of the invention 10 times at a dose corresponding to one tenth of the exposure giving the aforementioned maximum diffraction efficiency and a reference light angle varying by 2 degrees every recording job (first step). Thereafter, the hologram recording material was entirely irradiated with light having a wavelength of from 300 nm to 410 nm to perform recording amplification by polymerization (second step). As a result, it was confirmed that these object lights can be reproduced by irradiating the hologram recording material with a reproducing light at an angle varying by 2 degrees.
  • the hologram recording material of the invention can be subjected to multiplexed recording at the same exposure and thus is adapted for multiplexed recording.
  • the hologram recording material of the invention allows many multiplexed recording jobs and hence high density (capacity) recording.
  • the known photopolymer process hologram recording material as disclosed in JP-A-6-43634 was found to require more radiation dose in the latter stage of multiplexed recording than in the initial stage of multiplexed recording to perform the same recording because the polymerization of photopolymer has proceeded such that the rate of movement of monomer required for recording is reduced.
  • the known photopolymer process hologram recording material leaves something to be desired in the enhancement of multiplexity, Le., recording density.
  • the hologram recording method of the invention employs color development reaction as a means of forming a latent image rather than polymerization during hologram recording (first step) and thus is not subject to the aforementioned disadvantages. Therefore, the hologram recording method of the invention is superior to the known photopolymer process.
  • the lights with which the hologram recording material was entirely irradiated during the aforementioned procedure had an optimum wavelength in the respective system.
  • the sensitizing dye, electron-donating compound, discoloring agent precursor, discolorable dye and binder PMMA-EA (poly(methyl methacrylate-3% ethyl acrylate) copolymer; Mw: 101,000) set forth in Table 6 were dissolved in methylene chloride (optionally with acetone or acetonitrile) in an amount of twice to four times the weight of these components to prepare hologram recording material compositions 301 to 305.
  • the term "%" as used herein is meant to indicate wt-% based on the weight of binder PMMA-EA.
  • the hologram recording material compositions 301 to 305 were each spread (optionally in a multi-layer form) over a glass substrate to a thickness of about 80 ⁇ m using a blade to form a photosensitive layer which was then dried in vacuo at room temperature for one day to remove the solvent.
  • the photosensitive layer was then covered by TAC layer to prepare hologram recording materials 301 to 305,
  • the hologram recording materials were each then exposed to YAG laser second harmonic (532 nm; output: 2W) as a light source in a two-flux optical system for transmission hologram recording shown in Fig. 1 to perform recording.
  • the angle of the object light with respect to the reference light was 30 degrees.
  • the light had a diameter of 0.6 cm and an intensity of 8 mW/cm 2 .
  • the holographic exposure time was varied from 0.1 to 400 seconds (radiation energy ranging from 0.8 to 3,200 mJ/cm 2 ).
  • He-Ne laser beam having a wavelength of 632 nm was passed through the center of exposed area at the Bragg angle.
  • the ratio of diffracted light to transmitted light was then measured at real time. When a maximum diffraction efficiency was given, exposure was then suspended. Since the sensitizing dye shows no absorption at 632 nm, the hologram recording material is not sensitive to He-Ne laser beam.
  • the hologram recording materials were each then entirely irradiated with ultraviolet rays to visible light having a wavelength range of from 300 to 410 nm from a xenon lamp through a band pass filter so that the sensitizing dye was optically self-discolond to undergo fixation. Also during fixation, a He-Ne laser beam having a wavelength of 632 nm was passed through the center of the exposed area at the Bragg angle. The ratio of diffracted light to incident light (absolute diffraction efficiency) was measured at real time.
  • the hologram recording materials were each irradiated with reproducing light which is the same as the reference light having a wavelength of 532 nm used during recording.
  • the ratio of diffracted light to incident light was then measured.
  • the comparative example which is known in JP-A-6-43634, exhibits a high absolute diffraction efficiency at 632 nm but shows a shrinkage as great as more than 5% during recording because it employs a photopolymer process involving radical polymerization.
  • the comparative example shows an extremely deteriorated S/N ratio when used as holographic memory. Thus, the comparative example is not suitable for this purpose.
  • the comparative example exhibits a low absolute diffraction efficiency at 532 because the sensitizing dye cannot be fully decomposed and the remaining sensitizing dye absorbs reproducing light.
  • the inventive hologram recording materials 301 to 305 employ a recording process which is quite different from the known hologram recording process, i.e., hologram recording process involving refractive index modulation by discoloration reaction rather than by the movement and polymerization of material.
  • the inventive hologram recording materials 301 to 305 can perform recording at a shrinkage as extremely small as 0.01% or less and thus are suitable particularly for holographic memory.
  • the inventive hologram recording materials 301 to 305 can be optically self-discolored at the fixing step and thus exhibit no absorption at 532 nm.
  • the inventive hologram recording materials give a high absolute diffraction efficiency at 632 nm as well as at 532 nm to advantage.
  • the inventive hologram recording materials 301 to 305 showed no drop of diffraction efficiency.
  • inventive hologram recording materials show a substantially linear rise of ⁇ n (calculated from modulation of refractive index in interference fringes, diffraction efficiency and layer thickness on the basis of Kugelnick's equation) with exposure (mJ/cm 2 ) and thus are advantageous in multiplexed recording.
  • the known photopolymer process hologram recording material as disclosed in JP-A-6-43634 was found to require more radiation dose in the latter stage of multiplexed recording than in the initial stage of multiplexed recording to perform the same recording because the polymerization of photopolymer has proceeded such that the rate of movement of monomer required for recording is reduced.
  • the known photopolymer process hologram recording material leaves something to be desired in the enhancement of multiplexity, i.e., recording density.
  • sensitizing dye, electron-donating compound, discolorable dye, discoloring agent precursor, polymerisation initiator, polymerizable compound and binder set forth in Table 8 were dissolved in a double to quintuple amount of methylene chloride (optionally acetone, acetonitrile or methanol in a small portion as well) under a red light to prepare hologram recording materials 401 to 404.
  • methylene chloride optionally acetone, acetonitrile or methanol in a small portion as well
  • the hologram recording material compositions 401 to 404 were each spread (optionally in a multi-layer form) over a glass substrate to a thickness of about 80 ⁇ m using a blade to form a photosensitive layer which was then dried at room temperature in vacuo for 1 day to remove the solvent. The photosensitive layer was then covered by TAC layer to prepare hologram recording materials 401 to 404.
  • the hologram recording materials were each then exposed to YAG laser second harmonic (532 nm; output: 2W) as a light source in a two-flux optical system for transmission hologram recording shown in Fig. I to perform recording.
  • the angle of the object light with respect to the reference light was 30 degrees.
  • the light had a diameter of 0.6 cm and an intensity of 8 mW/cm 2 .
  • the holographic exposure time was varied from 0.1 to 40 seconds (radiation energy ranging from 0.8 to 320 mJ/cm 2 ) (first step).
  • He-Ne laser beam having a wavelength of 632 nm was passed through the center of exposed area at the Bragg angle.
  • the ratio of diffracted light to incident light was then measured at real time (diffraction efficiency ⁇ after first step).
  • the hologram recording material is not sensitive to He-Ne laser beam.
  • the hologram recording materials were each then entirely irradiated with light rays having a wavelength range of from 300 to 410 nm from a xenon lamp through a band pass filter (second step).
  • the absolute diffraction efficiency was measured at 632 nm and 532 nm (diffraction efficiency ⁇ after second step).
  • the radiation dose required at the first step can be reduced to one seventh to one fifth of that required when the second step is not employed.
  • the second step allows block exposure and hence polymerization with the discolorable dye left undiscolored at the first step as a latent image, resulting in amplification of refractive index modulation that allows the reduction of the first step, i.e., enhancement of sensitivity.
  • the known hologram recording material disclosed in JP-A-6-43634 cannot undergo such amplification that allows enhancement of sensitivity.
  • the inventive hologram recording material shows no absorption at 532 nm and thus gives a high absolute diffraction efficiency at 632 nm as well as at 532 nm.
  • the inventive hologram recording materials 401 to 404 When irradiated with light having a wavelength of 532 nm as reproducing light for 10 hours, the inventive hologram recording materials 401 to 404 showed no drop of diffraction efficiency. After one month of storage at room temperature, the inventive hologram recording materials 401 to 404 were each then measured for diffraction efficiency. As a result, these inventive hologram recording materials showed no special drop of diffraction efficiency.
  • the hologram recording material of the invention shows a substantially linear rise of ⁇ n (refractive index modulation in interference fringes, calculated from diffraction efficiency and layer thickness by Kugelnick's equation) with exposure (mJ/cm 2 ) both after the first and second steps and thus is favorable for multiplexed recording.
  • Multiplexed hologram recording was actually made on the same area of a hologram recording material of the invention 10 times at a dose corresponding to one tenth of the exposure giving the aforementioned maximum diffraction efficiency and a reference light angle varying by 2 degrees every recording job (first step). Thereafter, the hologram recording material was entirely irradiated with light having a wavelength of from 300 nm to 410 nm to perform recording amplification by polymerization (second step). As a result, it was confirmed that these object lights can be reproduced by irradiating the hologram recording material with a reproducing light at an angle varying by 2 degrees.
  • the hologram recording material of the invention can be subjected to multiplexed recording at the same exposure and thus is adapted for multiplexed recording.
  • the hologram recording material of the invention allows many multiplexed recording jobs and hence high density (capacity) recording.
  • the known photopolymer process hologram recording material as disclosed in JP-A-6-43634 was found to require more radiation dose in the latter stage of multiplexed recording than in the initial stage of multiplexed recording to perform the same recording because the polymerization of photopolymer has proceeded such that the rate of movement of monomer required for recording is reduced.
  • the known photopolymer process hologram recording material leaves something to be desired in the enhancement of multiplexity, i.e., recording density.
  • the hologram recording method of the invention employs color development reaction as a means of forming a latent image rather than polymerization during hologram recording (first step) and thus is not subject to the aforementioned disadvantages. Therefore, the hologram recording method of the invention is superior to the known photopolymer process.
  • discoloring agent precursor (acid generator, which optionally acts also as acid or radical polymerization initiator) to be used in Samples 301 to 304, 401 and 402 were changed to I-3, I-4, I-6 to 1-10, 4-(octylphenyl)pbenyl iodonium hexafluoroantimonate, tris(4-methylphenyl)sulfonium tetra (pentafluorophenyl)borate, triphenylsulfonium perfluoropentanoate, bis(1-(4-diphenylsulfonium) phenylsulfide ditrifurate, dimethylphenasyl sulfonium perfluorobutane sulfonate or benzoyl tosylate 1-22, I-23 or when the acid-discolorable dye to be used in Samples 301 to 304, 401 and 402 were changed to G-14, G-17, G-21,
  • the lights with which the hologram recording material was entirely irradiated during the aforementioned procedure had an optimum wavelength in the respective system.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Holo Graphy (AREA)
EP06003725A 2005-02-23 2006-02-23 Matériau pour l'enregistrement d'hologrammes, procédé d'enregistrement d'hologrammes, support d'enregistrement optique, et colorant correspondant Withdrawn EP1696265A2 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2005047339 2005-02-23

Publications (1)

Publication Number Publication Date
EP1696265A2 true EP1696265A2 (fr) 2006-08-30

Family

ID=36581583

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06003725A Withdrawn EP1696265A2 (fr) 2005-02-23 2006-02-23 Matériau pour l'enregistrement d'hologrammes, procédé d'enregistrement d'hologrammes, support d'enregistrement optique, et colorant correspondant

Country Status (2)

Country Link
US (1) US20060188789A1 (fr)
EP (1) EP1696265A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1696266A3 (fr) * 2005-02-25 2010-06-30 FUJIFILM Corporation Matériau d'enregistrement d'hologrammes et support d'enregistrement optique

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7582390B2 (en) * 2003-05-23 2009-09-01 Fujifilm Corporation Two-photon absorbing polymerization method, two-photon absorbing optical recording material and two-photon absorbing optical recording method
JP2005309359A (ja) * 2004-03-25 2005-11-04 Fuji Photo Film Co Ltd ホログラム記録材料、ホログラム記録方法、光記録媒体、３次元ディスプレイホログラムおよびホログラフィック光学素子。
JP2005275273A (ja) * 2004-03-26 2005-10-06 Fuji Photo Film Co Ltd ホログラム記録材料、ホログラム記録方法及び光記録媒体
JP4436737B2 (ja) * 2004-09-10 2010-03-24 富士フイルム株式会社 ２光子吸収消色材料、２光子吸収屈折率変調材料、２光子吸収重合材料、２光子吸収重合方法、及び３次元光記録材料
US20060057467A1 (en) * 2004-09-16 2006-03-16 Fuji Photo Film Co., Ltd. Hologram recording material and hologram recording method
JP4649158B2 (ja) * 2004-09-30 2011-03-09 富士フイルム株式会社 ホログラム記録方法
US8039076B2 (en) * 2006-12-27 2011-10-18 Industrial Technology Research Institute Dye and recording media utilizing the same
JP2012083409A (ja) * 2010-10-07 2012-04-26 Tdk Corp カラーホログラム画像記録用フォトポリマー媒体及びカラーホログラム画像記録方法

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB638496I5 (fr) * 1945-12-29
US2481464A (en) * 1945-12-29 1949-09-06 Gen Aniline & Film Corp Photographic emulsions containing nu-aryloxy-, arylthio-and arylselenoalkyl cyanine dyes
US2536973A (en) * 1947-06-21 1951-01-02 Gen Aniline & Film Corp Sensitizing cyanine dyestuff intermediates
US2553494A (en) * 1950-04-12 1951-05-15 Gen Aniline & Film Corp Merocyanine dyes containing an aryloxy-, arylthio-, or arylselenoalkyl group attached to one of the nitrogen atoms thereof
BE532103A (fr) * 1953-09-25 1900-01-01
US3574631A (en) * 1966-11-09 1971-04-13 Ferrania Spa Apomerocyanine dyes and photographic emulsions sensitized therewith
US3745009A (en) * 1968-10-09 1973-07-10 Eastman Kodak Co Photographic elements and light-absorbing layers
JP2663033B2 (ja) * 1990-02-22 1997-10-15 富士写真フイルム株式会社 ハロゲン化銀乳剤
JP2955803B2 (ja) * 1992-07-22 1999-10-04 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
US5763153A (en) * 1995-10-09 1998-06-09 Fuji Photo Film Co. Ltd Photothermographic material
JP3606998B2 (ja) * 1996-04-25 2005-01-05 富士写真フイルム株式会社 熱現像感光材料
US6582892B2 (en) * 2001-06-29 2003-06-24 Eastman Kodak Company Heat-stabilized IR-sensitive thermally developable imaging materials
US7582390B2 (en) * 2003-05-23 2009-09-01 Fujifilm Corporation Two-photon absorbing polymerization method, two-photon absorbing optical recording material and two-photon absorbing optical recording method
US7771915B2 (en) * 2003-06-27 2010-08-10 Fujifilm Corporation Two-photon absorbing optical recording material and two-photon absorbing optical recording and reproducing method
JP4411153B2 (ja) * 2003-07-18 2010-02-10 富士フイルム株式会社 ２光子吸収色素消色材料、３次元的屈折率変調材料、３次元吸収率変調材料及び３次元光記録材料
US20050046915A1 (en) * 2003-08-22 2005-03-03 Fuji Photo Film Co., Ltd. Hologram recording material composition, hologram recording material and hologram recording method
JP4393236B2 (ja) * 2004-03-15 2010-01-06 富士フイルム株式会社 硬化性組成物及びそれを用いた画像形成材料
JP2005309359A (ja) * 2004-03-25 2005-11-04 Fuji Photo Film Co Ltd ホログラム記録材料、ホログラム記録方法、光記録媒体、３次元ディスプレイホログラムおよびホログラフィック光学素子。
JP4436737B2 (ja) * 2004-09-10 2010-03-24 富士フイルム株式会社 ２光子吸収消色材料、２光子吸収屈折率変調材料、２光子吸収重合材料、２光子吸収重合方法、及び３次元光記録材料
US20060057467A1 (en) * 2004-09-16 2006-03-16 Fuji Photo Film Co., Ltd. Hologram recording material and hologram recording method
JP4649158B2 (ja) * 2004-09-30 2011-03-09 富士フイルム株式会社 ホログラム記録方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1696266A3 (fr) * 2005-02-25 2010-06-30 FUJIFILM Corporation Matériau d'enregistrement d'hologrammes et support d'enregistrement optique

Also Published As

Publication number Publication date
US20060188789A1 (en) 2006-08-24

Similar Documents

Publication Publication Date Title
US7572555B2 (en) Hologram recording material, hologram recording method and optical recording medium
EP1510862A2 (fr) Procédé d'enregistrement d'hologrammes et matériau pour l'enregistrement d'hologrammes
EP1696266A2 (fr) Matériau d'enregistrement d'hologrammes et support d'enregistrement optique
EP1626309B1 (fr) Matériau pour l'enregistrement de hologrammes, méthode pour l'enregistrement de hologrammes et élément optique holographique
EP1580597A2 (fr) Matériau pour l'enregistrement de hologrammes, méthode pour l'enregistrement de hologrammes et support d'enregistrement optique
US20070207390A1 (en) Hologram recording material and hologram recording method
EP1508833A2 (fr) Composition pour l'enregistrement d'hologrammes, matériau pour l'enregistrement d'hologrammes et méthode pour l'enregistremnt d'hologrammes
US20060188790A1 (en) Hologram recording material, hologram recording method, and optical recording medium
EP1696265A2 (fr) Matériau pour l'enregistrement d'hologrammes, procédé d'enregistrement d'hologrammes, support d'enregistrement optique, et colorant correspondant
JP4516813B2 (ja) ホログラム記録材料及びホログラム記録方法
JP4636823B2 (ja) ２光子吸収光記録材料、それを用いた２光子吸収光記録方法及び２光子吸収光記録再生方法
JP4431429B2 (ja) ホログラム記録材料、ホログラム記録方法及び光記録媒体
JP2005017354A (ja) ホログラム記録材料用組成物、ホログラム記録材料及びホログラム記録方法。
JP2005017730A (ja) ホログラム記録材料用組成物、ホログラム記録材料及びホログラム記録方法。
JP2006078821A (ja) ホログラム記録材料、ホログラム記録方法及び光記録媒体
JP4686380B2 (ja) ホログラム記録材料、ホログラム記録方法、及び光記録媒体
JP2005099751A (ja) ホログラム記録材料用組成物、ホログラム記録材料及びホログラム記録方法。
JP2008275671A (ja) ホログラフィック記録用組成物、ホログラフィック記録媒体、情報記録方法、および酸発生促進剤
JP2007262155A (ja) ２光子吸収光記録材料、２光子吸収光記録方法、２光子吸収光記録再生方法、２光子吸収光記録媒体及び２光子吸収光記録方法
JP4512446B2 (ja) ホログラム記録方法およびホログラム記録材料
JP2006268030A (ja) ホログラム記録材料、ホログラム記録再生方法及びホログラム記録方法、光記録媒体、光記録媒体への記録方法、それらに用いられる色素
JP2007233165A (ja) ホログラム記録材料、ホログラム記録方法及び光記録媒体
JP2006078877A (ja) ホログラム記録材料、ホログラム記録方法及び光記録媒体
JP2011095760A (ja) ホログラム記録材料、ホログラム記録方法、及び光記録媒体
JP2005099087A (ja) ホログラム記録材料及びホログラム記録方法。

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FUJIFILM CORPORATION

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20080901